Flame retardant poly(siloxane) copolymer compositions, methods of manufacture, and articles formed therefrom

ABSTRACT

A poly(siloxane) copolymer composition comprising: a first polymer comprising a first repeating unit, and a poly(siloxane) block unit, a second polymer different from the first polymer and comprising of bromine; and optionally, one or more third polymers different from the first polymer and second polymer; wherein siloxane units are present in the composition in an amount of at least 0.3 wt %, and bromine is present in the composition in an amount of at least 7.8 wt %, each based on the sum of the wt % of the first, second, and optional one or more third polymers; and further wherein an article molded from the composition has an OSU integrated 2 minute heat release test value of less than 65 kW-min/m 2  and a peak heat release rate of less than 65 kW/m 2 , and an E662 smoke test D max  value of less than 200.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent application Ser. No.13/251,122, filed Sep. 30, 2011, which claims priority to U.S. patentapplication Ser. No. 13/207,930, filed Aug. 11, 2011, which claimspriority to India Patent Application No. 920/DEL/2011, filed Mar. 31,2011, the contents of both applications being incorporated by referenceherein in their entirety.

BACKGROUND OF THE INVENTION

This disclosure generally relates to polymer compositions, and moreparticularly to flame retardant poly(siloxane) copolymer compositionscontaining specific combinations of siloxane block copolymers.

Flame retardant (FR) polymers and polymer blends, for examplepolycarbonates and polycarbonate blends with UL V0 and 5V A and BUnderwriters Laboratories flammability ratings are widely prepared andused, especially in a wide variety of electrical and electronicapplications. Conversely, only a very limited set of polycarbonates areused in aircraft and other transportation applications particularlyinterior parts such as windows, partition walls, ceiling panels, cabinetwalls, storage compartments, galley surfaces, light panels, and thelike. All of these applications have stringent flammability safetyrequirements that the polycarbonates must meet. Particular requirementsinclude smoke density, flame spread, and heat release values. In theUnited States, Federal Aviation Regulation (FAR) Part 25.853 sets forththe airworthiness standards for aircraft compartment interiors. Thesafety standards for aircraft and transportation systems used in theUnited States include a smoke density test specified in FAR 25.5Appendix F, Part V Amdt 25-116. Flammability requirements include the“60 second test” specified in FAR 25.853(a) Appendix F, Part I,(a),1,(i) and the heat release rate standard (referred to as the OSU65/65 standard) described in FAR F25.4 (FAR Section 25, Appendix F, PartIV), or the French flame retardant tests such as, NF-P-92-504 (flamespread) or NF-P-92-505 (drip test). In another example, the aircraftmanufacturer Airbus has smoke density and other safety requirements setforth in ABD0031. In the event of a fire, components made from materialshaving these properties can increase the amount of time available forescape and provide for better visibility during a fire

Despite extensive investigation, current materials that meet these FARstandards could be further improved with respect to other properties.Thus, there is a perceived need for polysulfones having improved meltflow, improved ultraviolet (UV) stability, and improved lighttransmission. Siloxane-polyestercarbonates have low melt flow and goodcolor stability to indoor light, but may shift in color upon exposure toUV light. Certain polycarbonate-polyetherimide blends also have low meltflow, but can be difficult to formulate so as to provide bright whitecompositions.

In view of the current interior material safety standards and inanticipation of more stringent standards in the future, materials thatexceed governmental and aircraft manufacturer flame safety requirementsare sought. Such materials should also advantageously maintain excellentphysical properties, such as toughness (high impact strength and highductility). It would be a further advantage if such materials could bemanufactured to be colorless and transparent. Still other advantageousfeatures include good processability for forming articles, smoothsurface finish, and light stability.

BRIEF SUMMARY OF THE INVENTION

Disclosed herein is a composition comprising: A composition comprising:a first polymer comprising (a) a first repeating unit, and (b) apoly(siloxane) block unit, the poly(siloxane) block unit having theformula:

wherein R is each independently a C₁-C₃₀ hydrocarbon group, and E has anaverage value of 5 to 200; a second polymer different from the firstpolymer and comprising bromine; and optionally, one or more thirdpolymers different from the first polymer and second polymer; whereinthe wt % of the first polymer, second polymer, and optional one or morethird polymers sum to 100 wt %, siloxane units are present in thecomposition in an amount of at least 0.3 wt %, based on the sum of thewt % of the first, second, and optional one or more third polymers, andbromine is present in the composition in an amount of at least 7.8 wt %,based on the sum of the wt % of the first, second, and optional one ormore third polymers; and further wherein an article molded from thecomposition has an OSU integrated 2 minute heat release test value ofless than 65 kW-min/m² and a peak heat release rate of less than 65kW/m² as measured using the method of FAR F25.4, in accordance withFederal Aviation Regulation FAR 25.853 (d), and an E662 smoke testD_(max) value of less than 200 when measured at a thickness of 1.6 mm

Also described is a method of manufacture of the above-describedcompositions.

Articles comprising the above-described compositions are furtherdisclosed, as well as methods for the manufacture of the articles.

The above described and other features are exemplified by the followingDetailed Description and Examples.

DETAILED DESCRIPTION OF THE INVENTION

The inventors hereof have discovered that flame retardant, low smokecompositions comprising specific siloxane block copolymers canunexpectedly be obtained when certain siloxane-containing copolymercompositions and bromine-containing compositions, neither of which meetsstrict low density smoke standards, are used in combination. Inparticular, certain poly(siloxane) block copolymer compositions andcertain bromine-containing compositions, do not by themselves meetstrict low smoke density standards when burned. However, specificcombinations of these two compositions can meet low smoke densitystandards, and have very low heat release properties. Achieving very lowsmoke density and very low flammability ratings are conflictingrequirements. Halogenated, specifically brominated, flame retardants areused in poly(siloxane) copolymer compositions for their effectiveness inimproving flame spread properties and satisfying the stringent aircraftand rail interior flammability standards. Brominated flame retardantadditives, however, cause an increase in smoke when the sheetcompositions are ignited. It is therefore surprising that a brominatedflame retardant can be added to a poly(siloxane) block or graftcopolymer and lower the smoke density of the poly(siloxane) copolymer.

The compositions can further have excellent mechanical properties,including at least one of high impact strength, low brittleness (highductility) as well as favorable processing characteristics, such as lowmelt viscosity. In a further advantageous feature, the combinations canbe transparent. In another advantageous feature, the compositions canhave low density. Such compositions are especially useful in themanufacture of flame retardant, low smoke poly(siloxane) copolymersheets that can be used, for example, in aircraft, train, marine, orother transportation applications.

The compositions contain a first polymer comprising first repeatingunits and blocks of repeating polysiloxane units; a brominated secondpolymer different from the first polymer; and optionally, one or morethird polymers different from the first polymer and second polymer,wherein the weight percent (wt %) of the first polymer, second polymer,and optional one or more third polymers sum to 100 wt %, and thepolysiloxane units are present in the composition in an amount of atleast 0.3 wt %, based on the sum of the wt % of the first, second, andoptional third polymers, and bromine is present in the composition in anamount of at least 7.8 wt %, based on the sum of the wt % of the first,second, and optional third polymers; and further wherein an articlemolded from the composition has an OSU integrated 2 minute heat releasetest value of less than 65 kW-min/m² and a peak heat release rate ofless than 65 kW/m² as measured using the method of FAR F25.4, inaccordance with Federal Aviation Regulation FAR 25.853 (d), and an E662smoke test D_(max) value of less than 200 when measured at a thicknessof 1.6 mm. For simplicity, this test can be referred to herein as the“smoke density test.”

The first, second, and optionally one or more third polymers are furtherselected and used in amounts effective to satisfy the requirements forheat release rates described in FAR F25.4 (Federal Aviation RegulationsSection 25, Appendix F, Part IV). Materials in compliance with thisstandard are required to have a 2-minute integrated heat release rate ofless than or equal to 65 kilowatt-minutes per square meter (kW-min/m²)and a peak heat release rate of less than 65 kilowatts per square meter(kW/m²) determined using the Ohio State University calorimeter,abbreviated as OSU 65/65 (2 min/peak). In applications requiring a morestringent standards, where a better heat release rate performance iscalled for, a 2-minute integrated heat release rate of less than orequal to 55 kW-min/m² and a peak heat release rate of less than 55 kW/m²(abbreviated as OSU 55/55) may be required.

Without being bound by theory, it is believed that the unexpectedcombination of low smoke density and low heat release values obtained isachieved by careful selection and balancing of the absolute and relativeamounts of the first polymer, the second polymer, and the optional oneor more third polymers, including selecting an amount of first polymer,block size (i.e., length) of the siloxane blocks, and number of siloxaneblocks such that at least 0.3 wt % polysiloxane units are present in thecomposition; and selecting the type and amount of the second polymer andthe amount of bromine in the second polymer such that at least 7.8 wt %bromine is present in the composition . The compositions thereforeinclude amounts of the first and second polymers effective, i.e.,sufficient, to provide the desired amount of polysiloxane units andbromine, which in turn yields compositions having the an OSU-integrated2 minute heat release test value of less than 65 kW-min/m² and a peakheat release rate of less than 65 kW/m² as measured using the method ofFAR F25.4, in accordance with Federal Aviation Regulation FAR 25.853(d), and an E662 smoke test D_(max) value of less than 200 when testedat a thickness of 1.6 mm.

In an embodiment, an effective amount of the siloxane-containingcopolymer is at least 1 wt %, specifically 1 to 85 wt % of thesiloxane-containing copolymer, and an effective amount of the brominatedpolymer is at least 15 wt %, specifically 15 to 95 wt %, each based onthe total weight of the first polymer, second polymer, and optional oneor more third polymers. The precise amount of the first polymereffective to provide at least 0.3 wt % of the polysiloxane units dependson the selected copolymer, the length of the siloxane block, the numberthe siloxane-containing blocks, and the desired properties, such assmoke density, heat release values, transparency, impact strength, meltviscosity, and/or other desired physical properties. In general, to beeffective, when a block copolymer is used, the smaller the block sizeand/or the lower the number of blocks in the first polymer, the higherthe fractional concentration of the first polymer, based on the totalweight of the first, second and optionally one or more third polymers.When a graft copolymer is used, the lower the number of branches and/orthe shorter the branches, the higher is the fractional concentration ofthe first polymer based on the total weight of the first, second andoptionally one or more third polymers. Similarly, for the brominatedpolymer, the precise amount depends on the type of polymer, the amountof bromine in the polymer, and other desired characteristics of thecompositions. The lower the weight percent of bromine in the secondpolymer, the higher the fractional concentration of the second polymer,based on the total weight of the first, second and optionally one ormore third polymers. Thus, an effective amount of thesiloxane-containing copolymer in some embodiments can be at least 5 wt%, specifically 5 to 80 wt %, or at least 10 wt %, specifically 10 to 70wt %, or at least 15 wt %, specifically 15 to 60 wt %, and an effectiveamount of the brominated polymer in some embodiments can be at least 20wt %, specifically 20 to 85 wt %, or 20 to 75 wt %, each based on thetotal weight of the first polymer, second polymer, and optional one ormore third polymers.

As stated above, the first polymer comprises first repeating units andblocks of repeating polysiloxane units. In a particularly advantageousfeature, the first repeating units can be a variety of different units,which allows manufacture of low smoke, low heat release compositionshaving a variety of properties. The first repeating units can bepolycarbonate units, etherimide units, ester units, sulfone units, ethersulfone units, arylene ether sulfone units, arylene ether units, andcombinations comprising at least one of the foregoing, for exampleresorcinol-based aryl ester-carbonate units, etherimide-sulfone units,and arylene ether-sulfone units.

In a specific embodiment, the first, second, and optional third polymersare polycarbonates, that is, polymers containing repeating carbonateunits. Thus the first polymer is a poly(siloxane-carbonate) copolymer,the second polymer is a brominated polymer containing repeatingcarbonate units, and the one or more optional third polymers arepolycarbonate homopolymers or copolymers. In an embodiment, thepolycarbonate composition comprises at least 5 wt %, specifically 5 to85 wt % of the first poly(siloxane-carbonate) copolymer, at least 15 wt%, specifically 15 to 95 wt % of the second brominated polycarbonate,such as a brominated polycarbonate derived from2,2′,6,6′-tetrabromo-4,4′-isopropylidenediphenol(2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane(TBBPA) and carbonate units derived from at least one dihydroxy aromaticcompound that is not TBBPA (“TBBPA copolymer”), and 0 to 70 wt % of theoptional one or more third polymers, based on the total weight of thefirst, second, and optional one or more third polymers, i.e., the wt %of the first polymer, second polymer, and optional one or more thirdpolymers sum to 100 wt %. The siloxane blocks present in the firstpolymer have an average of 5 to 200 units, specifically 5 to 100 units.At least 0.3 wt % siloxane and at least 7.8 wt % bromine is present,each based on total weight of the first polymer, second polymer, andoptional one or more third polymers.

Further in this embodiment, when the siloxane blocks have an average of25 to 75 units, specifically 25 to 50 units, and at least 2.0 wt %siloxane is present based on total weight of the first polymer, secondpolymer, and optional one or more third polymers, excellent toughness isobtained, in particular an article molded from the composition furtherhas a room temperature notched Izod impact of greater than 500 J/m asmeasured according to ASTM D 256-10 at a 0.125 inch (3.2 mm) thickness.The articles can further have 100% ductility. The amount of siloxane inthe composition can be varied by controlling the length of units perblock, the number of blocks and the tacticity of the blocks along thebackbone.

Still further in this embodiment, when the polysiloxane units of thefirst polymer is present in an amount of at least 2.0 wt % and thecomposition has 35 to 50 wt % of the second polymer (the TBBPAcopolymer), each based on total weight of the first polymer, secondpolymer, and optional one or more third polymers, and the siloxaneblocks have an average length of 25 to 50 units, excellent transparencycan be obtained, in particular an article molded from this compositionhas a haze of less than 10% and a transmission greater than 70%, eachmeasured using the color space CIE1931 (Illuminant C and a 2° observer),or according to ASTM D 1003 (2007) using illuminant C at a 0.125 inch(3.2 mm) thickness.

Excellent transparency can also be obtained when the polycarbonatecomposition comprises the first polymer in an amount effective toprovide at least 0.3 wt % siloxane and the second polymer in an amounteffective to provide at least 5.0 wt % bromine, each based on totalweight of the first polymer, second polymer, and optional one or morethird polymers, and the siloxane blocks or grafts have an average of 5to 75, specifically 5 to 15 units. Effective amounts can be at least 30wt %, specifically 30 to 80 wt % of the first polymer, and at least 20wt %, specifically at least 20 to 50 wt % of the second polymer (theTBBPA copolymer), and 0 to 50 wt % of the optional one or more thirdpolymers, each based on the total weight of the first, second, andoptionally one or more third polymers. An article molded from thecomposition has a haze of less than 3% and a transmission greater than85%, each measured using the color space CIE1931 (Illuminant C and a 2°observer), or according to ASTM D 1003 (2007) using illuminant C at a0.062 inch (1.5 mm) thickness.

In still other embodiments, it has been found that limiting the amountof the optional third polymer, together with use of specific first andsecond polycarbonates can produce compositions with advantageousproperties. In one such embodiment, the polycarbonate compositioncomprises the first polymer (the poly(siloxane-carbonate)), the secondpolymer (the TBBPA copolymer or brominated oligomer), and 8 to 12 wt %of the one or more third polymers, wherein the wt % of the firstpolymer, second polymer, and one or more third polymers sum to 100 wt %based on the total weight of the first, second and optionally one ormore third polymers. The siloxane blocks have an average value of 20 to85 units. At least 0.4 wt % of siloxane and at least 7.8 wt % of bromineis present, each based on total weight of the first polymer, secondpolymer, and one or more third polymers. In an embodiment, thepolycarbonate composition comprises 5 to 60 wt % of the firstpoly(siloxane-carbonate) 30 to 60 wt % of the second polymer (the TBBPAcopolymer).

In an alternative embodiment of the polycarbonate compositions, it hasbeen found that other brominated oligomers can be used in place of theTBBPA copolymer, such as other brominated polycarbonate oligomers orbrominated epoxy oligomers. In this embodiment, the polycarbonatecompositions contain the first poly(siloxane-carbonate), a brominatedoligomer, and an optional additional polycarbonate different from thefirst polymer and the brominated oligomer. The optional additionalpolycarbonate can be the same as the optional one or more third polymersdescribed in the above embodiments. The first polymer, the brominatedoligomer, and the optional additional polycarbonate are present inamounts effective to provide at least 0.4 wt % of siloxane and at least7.8 wt % of bromine, each based on total weight of the first polymer,brominated oligomer, and additional polycarbonate, and thus satisfy atleast the smoke density test and the heat release OSU 65/65 test. Inparticular, the polycarbonate compositions comprise at least 5 wt %,specifically 5 to 85 wt % of the first poly(siloxane-carbonate), atleast 15 wt %, specifically at least 15 to 95 wt % of the brominatedoligomer, and 0 to 60 wt % of the optional additional polycarbonate,each based on the total weight of the first polymer, brominatedoligomer, and optional additional polycarbonate. The siloxane blockshave an average of 5 to 100 units.

While the smoke density and OSU tests demonstrate the ability of thepoly(siloxane) copolymer compositions described herein to comply withboth the smoke generation and heat release requirements fortransportation components, particularly aircraft or train interiors, anyof the above-described compositions can advantageously comply with otherrelated flammability and safety tests as described above.

In certain embodiments, the first, second, and optional one or morethird polymers, as well as the brominated polycarbonates (including theTBBPA copolymer and brominated polycarbonate oligomers) have repeatingstructural carbonate units of formula (1):

wherein at least 60%, specifically at least 80%, and specifically atleast 90% of the total number of R¹ groups contains aromatic organicgroups and the balance thereof are aliphatic or alicyclic groups. Inparticular, use of aliphatic groups is minimized in order to maintainthe flammability performance of the polycarbonates. In an embodiment, atleast 70%, at least 80%, or 95 to 100% of the R¹ groups are aromaticgroups. In an embodiment, each R¹ is a divalent aromatic group, forexample derived from an aromatic dihydroxy compound of formula (2):

HO-A¹-Y¹-A²-OH   (2)

wherein each of A¹ and A² is independently a monocyclic divalent arylenegroup, and Y¹ is a single bond or a bridging group having one or twoatoms that separate A¹ from A². In an embodiment, one atom separates A¹from A². In another embodiment, when each of A¹ and A² is phenylene, Y¹is para to each of the hydroxyl groups on the phenylenes. Illustrativenon-limiting examples of groups of this type are —O—, —S—, —S(O)—,—S(O)₂—, —C(O)—, methylene, cyclohexyl-methylene,2-[2.2.1]-bicycloheptylidene, ethylidene, isopropylidene,neopentylidene, cyclohexylidene, cyclopentadecylidene,cyclododecylidene, and adamantylidene. The bridging group Y¹ can be ahydrocarbon group, specifically a saturated hydrocarbon group such asmethylene, cyclohexylidene, or isopropylidene.

Included within the scope of formula (2) are bisphenol compounds offormula (3):

wherein each of R^(a) and R^(b) is independently a halogen atom or amonovalent hydrocarbon group; p and q are each independently integers of0 to 4; and X^(a) represents a single bond or one of the groups offormulas (4) or (5):

wherein each R^(e) and R^(d) is independently hydrogen, C₁₋₁₂ alkyl,C₁₋₁₂ cycloalkyl, C₇₋₁₂ arylalkyl, C₁₋₁₂ heteroalkyl, or cyclic C₇₋₁₂heteroarylalkyl, and Re is a divalent C₁₋₁₂ hydrocarbon group. Inparticular, R^(c) and R^(d) are each the same hydrogen or C₁₋₄ alkyl,specifically the same C₁₋₃ alkyl, even more specifically, methyl.

In an embodiment, R^(c) and R^(d) taken together is a C₃₋₂₀ cyclicalkylene or a heteroatom-containing C₃₋₂₀ cyclic alkylene comprisingcarbon atoms and heteroatoms with a valency of two or greater. Thesegroups can be in the form of a single saturated or unsaturated ring, ora fused polycyclic ring system wherein the fused rings are saturated,unsaturated, or aromatic. A specific heteroatom-containing cyclicalkylene group comprises at least one heteroatom with a valency of 2 orgreater, and at least two carbon atoms. Heteroatoms in theheteroatom-containing cyclic alkylene group include —O—, —S—, and—N(Z)—, where Z is a substituent selected from hydrogen, hydroxy, C₁₋₁₂alkyl, C₁₋₁₂ alkoxy, or C₁₋₁₂ acyl.

In a specific embodiment, X^(a) is a substituted C₃₋₁₈ cycloalkylideneof formula (6):

wherein each R^(r), R^(p), R^(q), and R^(t) is independently hydrogen,halogen, oxygen, or C₁₋₁₂ organic group; I is a direct bond, a carbon,or a divalent oxygen, sulfur, or —N(Z)— wherein Z is hydrogen, halogen,hydroxy, C₁₋₁₂ alkyl, C₁₋₁₂ alkoxy, or C₁₋₁₂ acyl; h is 0 to 2, j is 1or 2, i is an integer of 0 or 1, and k is an integer of 0 to 3, with theproviso that at least two of R^(r), R^(p), R^(q), and R^(t) takentogether are a fused cycloaliphatic, aromatic, or heteroaromatic ring.It will be understood that where the fused ring is aromatic, the ring asshown in formula (6) will have an unsaturated carbon-carbon linkagewhere the ring is fused. When k is 1 and i is 0, the ring as shown informula (6) contains 4 carbon atoms, when k is 2, the ring as showncontains 5 carbon atoms, and when k is 3, the ring contains 6 carbonatoms. In an embodiment, two adjacent groups (e.g., R^(q) and R^(t)taken together) form an aromatic group, and in another embodiment, R^(q)and R^(t) taken together form one aromatic group and R^(r) and R^(p)taken together form a second aromatic group.

When k is 3 and i is 0, bisphenols containing substituted orunsubstituted cyclohexane units are used, for example bisphenols offormula (7):

wherein R^(f) is each independently hydrogen, C₁₋₁₂ alkyl, or halogen;and R^(g) is each independently hydrogen or C₁₋₁₂ alkyl. Thesubstituents can be aliphatic or aromatic, straight chain, cyclic,bicyclic, branched, saturated, or unsaturated. Suchcyclohexane-containing bisphenols, for example the reaction product oftwo moles of a phenol with one mole of a hydrogenated isophorone, areuseful for making polycarbonate polymers with high glass transitiontemperatures (T_(g)) and high heat distortion temperatures (HDT).Cyclohexyl bisphenol-containing polycarbonates, or a combinationcomprising at least one of the foregoing with other bisphenolpolycarbonates, are supplied by Bayer Co. under the APEC® trade name.

Other useful dihydroxy compounds having the formula HO—R¹—OH includearomatic dihydroxy compounds of formula (8):

wherein R^(h) is each independently a halogen atom, a C₁₋₁₀ hydrocarbylsuch as a C₁₋₁₀ alkyl group, a halogen substituted C_(i-io) hydrocarbylsuch as a halogen-substituted C₁₋₁₀ alkyl group, and h is 0 to 4. Thehalogen is usually bromine.

Some illustrative examples of dihydroxy compounds include the following:4,4′-dihydroxybiphenyl, 1,6-dihydroxynaphthalene,2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane,bis(4-hydroxyphenyl)diphenylmethane,bis(4-hydroxyphenyl)-1-naphthylmethane, 1,2-bis(4-hydroxyphenyl)ethane,1,1-bis(4-hydroxyphenyl)-1-phenylethane,2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane,bis(4-hydroxyphenyl)phenylmethane,2,2-bis(4-hydroxy-3-bromophenyl)propane,1,1-bis(hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxyphenyl)isobutene,1,1-bis(4-hydroxyphenyl)cyclododecane,trans-2,3-bis(4-hydroxyphenyl)-2-butene,2,2-bis(4-hydroxyphenyl)adamantine, alpha,alpha'-bis(4-hydroxyphenyl)toluene, bis(4-hydroxyphenyl)acetonitrile,2,2-bis(3-methyl-4-hydroxyphenyl)propane,2,2-bis(3-ethyl-4-hydroxyphenyl)propane,2,2-bis(3-n-propyl-4-hydroxyphenyl)propane,2,2-bis(3-isopropyl-4-hydroxyphenyl)propane,2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane,2,2-bis(3-t-butyl-4-hydroxyphenyl)propane,2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,2,2-bis(3-allyl-4-hydroxyphenyl)propane,2,2-bis(3-methoxy-4-hydroxyphenyl)propane,2,2-bis(4-hydroxyphenyl)hexafluoropropane,1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dibromo-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dichloro-2,2-bis(5-phenoxy-4-hydroxyphenyl)ethylene,4,4′-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone,1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, ethylene glycolbis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether,bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide,bis(4-hydroxyphenyl)sulfone, 9,9 to bis(4-hydroxyphenyl)fluorine,2,7-dihydroxypyrene,6,6′-dihydroxy-3,3,3′,3′-tetramethylspiro(bis)indane (“spirobiindanebisphenol”), 3,3-bis(4-hydroxyphenyl)phthalide,2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene,2,7-dihydroxyphenoxathin, 2,7-dihydroxy-9,10-dimethylphenazine,3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and2,7-dihydroxycarbazole, resorcinol, substituted resorcinol compoundssuch as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol,5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl resorcinol, 5-cumylresorcinol, 2,4,5,6-tetrafluoro resorcinol, 2,4,5,6-tetrabromoresorcinol, and the like; catechol; hydroquinone; and substitutedhydroquinones such as 2-methyl hydroquinone, 2-ethyl hydroquinone,2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone,2-phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra-t-butyl hydroquinone, 2,3,5,6-tetrafluorohydroquinone, 2,3,5,6-tetrabromo hydroquinone, and the like.Combinations comprising at least one of the foregoing dihydroxycompounds can be used.

Specific examples of bisphenol compounds that can be represented byformula (3) include 1,1-bis(4-hydroxyphenyl) methane,1,1-bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl)propane(bisphenol A or BPA), 2,2-bis(4-hydroxyphenyl) butane,2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)propane,1,1-bis(4-hydroxyphenyl)n-butane,2,2-bis(4-hydroxy-l-methylphenyl)propane,1,1-bis(4-hydroxy-t-butylphenyl)propane,3,3-bis(4-hydroxyphenyl)phthalimidine,2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine (PPPBP), and1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (DMBPC). Combinationscomprising at least one of the foregoing dihydroxy compounds can also beused.

“Polycarbonate” as used herein includes homopolycarbonates, copolymerscomprising different R¹ moieties in the carbonate (“copolycarbonates”),and copolymers comprising carbonate units and other types of polymerunits, such as polysiloxane units or ester units. In a specificembodiment, the one or more optional third polymers is a linearhomopolymer or copolymer comprising units derived from bisphenol A, inwhich each of A¹ and A² is p-phenylene and Y¹ is isopropylidene informula (2). More specifically, at least 60%, particularly at least 80%of the R¹ groups in the polycarbonate homopolymer or copolymer arederived from bisphenol A. In an embodiment, the first polymer is a blockor graft copolymer comprising carbonate units of formula (1) and blocksof polysiloxane units, i.e., a poly(siloxane-co-carbonate), referred toherein as a “poly(siloxane-carbonate).” Block poly(siloxane-carbonate)copolymers comprise siloxane blocks and carbonate blocks in the polymerbackbone. Graft poly(siloxane-carbonate) copolymers are non-linearcopolymers comprising the siloxane blocks connected to linear or branchpolymer backbone comprising carbonate blocks.

In addition to the first repeating units in the first polymer (forexample polycarbonate units (1) as described above), the first polymercomprises blocks of polysiloxane units of formula (9):

wherein R is each independently a C₁-C₃₀ hydrocarbon group, specificallya C₁₋₁₃ alkyl group, C₂₋₁₃ alkenyl group, C₃₋₆ cycloalkyl group, C₆₋₁₄aryl group, C₇₋₁₃ arylalkyl group, or C₇₋₁₃ alkylaryl group. Theforegoing groups can be fully or partially halogenated with fluorine,chlorine, bromine, or iodine, or a combination comprising at least oneof the foregoing. Combinations of the foregoing R groups can be used inthe same copolymer. In an embodiment, the polysiloxane comprises Rgroups that have minimum hydrocarbon content. In yet another embodiment,the foregoing R groups are functionalized wherein at least one methylgroup has been replaced by another group, which is preferably nothydrogen, or wherein the functionalized R groups incorporate reactivefunctional groups such as anhydrides and epoxides that can react withother components by, for example, covalent bonding. In a specificembodiment, R is each the same and is a methyl group.

The average value of E in formula (9) can vary from 5 to 200. In anembodiment, E has an average value of 5 to 100, 10 to 100, 10 to 50, 25to 50, or 35 to 50. In another embodiment, E has an average value of 5to 75, specifically 5 to 15, specifically 5 to 12, more specifically 7to 12. The siloxane blocks can be atactic, isotactic, or syndiotactic.In an embodiment, the tacticity of the siloxane can affect the effectiveamount of each copolymer used. The siloxane containing copolymer can bea graft copolymer wherein the siloxane-containing blocks are branchedfrom a polymer backbone having blocks of the first repeating units, forexample carbonate units of formula (1).

In an embodiment, for example in poly(siloxane-carbonates), thepolysiloxane units can be derived from polysiloxane bisphenols offormula (10) or (11):

wherein E is as defined in formula (9); each R can be the same ordifferent, and is as defined in formula (9); each Ar can be the same ordifferent, and is a substituted or unsubstituted C₆₋₃₀ arylene group;and each R² is the same or different, and is a divalent C₁₋₃₀ alkyleneor C₇₋₃₀ arylenealkylene wherein the bonds of the hydroxyl groups aredirectly bonded to the arylene moiety or the alkylene moiety.

The Ar groups in formula (10) can be derived from a C₆₋₃₀ dihydroxyaromatic compound, for example a dihydroxy aromatic compound of formula(2), (3), (6), (7), or (8) above. Combinations comprising at least oneof the foregoing dihydroxy aromatic compounds can also be used.Illustrative examples of dihydroxy aromatic compounds are resorcinol(i.e., 1,3-dihydroxybenzene), 4-methyl-1,3-dihydroxybenzene,5-methyl-1,3-dihydroxybenzene, 4,6-dimethyl-1,3-dihydroxybenzene,1,4-dihydroxybenzene, 1,1-bis(4-hydroxyphenyl)methane,1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane,2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane,1,1-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)n-butane,2,2-bis(4-hydroxy-1-methylphenyl)propane,1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl sulfide), and1,1-bis(4-hydroxy-t-butylphenyl)propane. Combinations comprising atleast one of the foregoing dihydroxy compounds can also be used. In anembodiment, the dihydroxy aromatic compound is unsubstituted, or is notsubstituted with non-aromatic hydrocarbon-containing substituents suchas alkyl, alkoxy, or alkylene substituents.

In a specific embodiment, where Ar is derived from resorcinol, thepolydiorganosiloxane repeating units are derived from polysiloxanebisphenols of formula (12):

or, where Ar is derived from bisphenol A, from polvsiloxane bisphenolsof formula (13):

wherein E is as defined above.

Where R² is C₇₋₃₀ arylenealkylene in formula (11), the polysiloxaneunits can be derived from polysiloxane bisphenols of formula (14):

wherein R and E are as defined in formula (9). R³ is each independentlya divalent C₂₋₈ aliphatic group. Each M can be the same or different,and can be a halogen, cyano, nitro, C₁₋₈ alkylthio, C₁₋₈ alkyl, C₁₋₈alkoxy, C₂₋₈ alkenyl, C₂₋₈ alkenyloxy group, C₃₋₈ cycloalkyl, C₃₋₈cycloalkoxy, C₆₋₁₀ aryl, C₆₋₁₀ aryloxy, C₇₋₁₂ arylalkyl, C₇₋₁₂arylalkoxy, C₇₋₁₂ alkylaryl, or C₇₋₁₂ alkylaryloxy, wherein each n isindependently 0, 1, 2, 3, or 4. In an embodiment, M is bromo or chloro,an alkyl such as methyl, ethyl, or propyl, an alkoxy such as methoxy,ethoxy, or propoxy, or an aryl such as phenyl, chlorophenyl, or tolyl;R³ is a dimethylene, trimethylene or tetramethylene group; and R is aC₁₋₈ alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl suchas phenyl, chlorophenyl or tolyl. In another embodiment, R is methyl, ora combination of methyl and trifluoropropyl, or a combination of methyland phenyl. In still another embodiment, M is methoxy, n is 0 or 1, R³is a divalent C₁₋₃ aliphatic group, and R is methyl.

In a specific embodiment, the polysiloxane units are derived from apolysiloxane bisphenol of formula (15):

wherein E is as described in formula (9).

In another specific embodiment, the polysiloxane units are derived frompolysiloxane bisphenol of formula (16):

wherein E is as described in formula (9).

The relative amount of carbonate and polysiloxane units in thepoly(siloxane-carbonate) will depend on the desired properties, and arecarefully selected using the guidelines provided herein. In particular,as mentioned above, the block or graft poly(siloxane-carbonate)copolymer is selected to have a certain average value of E, and isselected and used in amount effective to provide the desired wt % ofpolysiloxane units in the composition. In an embodiment, thepoly(siloxane-carbonate) can comprise polysiloxane units in an amount of0.3 to 30 weight percent (wt %), specifically 0.5 to 25 wt %, or 0.5 to15 wt %, or even more specifically 0.7 to 8 wt %, or 0.7 to 7 wt %,based on the total weight of the poly(siloxane-carbonate), withremainder being carbonate units.

In an embodiment, the poly(siloxane-carbonate) comprises units derivedfrom polysiloxane bisphenols (14) as described above, specificallywherein M is methoxy, n is 0 or 1, R³ is a divalent C₁₋₃ aliphaticgroup, and R is methyl, still more specifically a polysiloxane bisphenolof formula (15) or (16). In these embodiments, E can have an averagevalue of 8 to 100, wherein the polysiloxane units are present in anamount of 0.3 to 25 wt % based on the total weight of thepoly(siloxane-carbonate); or, in other embodiments, E can have anaverage value of 25 to 100, wherein the polysiloxane units are presentin an amount of 5 to 30 wt % based on the total weight of thepoly(siloxane-carbonate); or E can have an average value of 30 to 50, or40 to 50, wherein the polysiloxane units are present in an amount of 4to 8 wt % based on the total weight of the poly(siloxane-carbonate); orE can have an average value of 5 to 12, wherein the polysiloxane unitsare present in an amount of 0.5 to 7 wt % based on the total weight ofthe poly(siloxane-carbonate).

In another embodiment, the first polymer is a poly(siloxane-etherimide)copolymer comprising siloxane blocks (9) and polyetherimide units offormula (17):

wherein a is 1 or greater than 1, for example 5 to 1,000 or more, ormore specifically 10 to 500. In this embodiment, the first polymer is ablock or graft copolymer comprising etherimide units of formula (17) andblocks of polysiloxane units, i.e., a poly(siloxane-co-etherimide),referred to herein as a “(polyetherimide-siloxane).” Blockpoly(siloxane-etherimide) copolymers comprise siloxane blocks andetherimide blocks in the polymer backbone. The siloxane blocks and thepolyetherimide units can be present in random order, as blocks (i.e.,AABB), alternating (i.e., ABAB), or a combination thereof Graftpoly(siloxane-etherimide) copolymers are non-linear copolymerscomprising the siloxane blocks connected to linear or branch polymerbackbone comprising etherimide blocks.

The group R in formula (17) is a divalent hydrocarbon group, such as aC₆₋₂₀ aromatic hydrocarbon group or halogenated derivative thereof, astraight or branched chain C₂₋₂₀ alkylene group or halogenatedderivative thereof, a C₃₋₂₀ cycloalkylene group or halogenatedderivative thereof, or a divalent group of formula (18):

wherein Q¹ is —O—, —S—, —C(O)—, —SO₂—, —SO—, and —C_(y)H_(2y)— and ahalogenated derivative thereof (which includes perfluoroalkylene groups)wherein y is an integer from 1 to 5. In a specific embodiment R is am-phenylene or p-phenylene.

The group Z in formula (17) is also a divalent hydrocarbon group, andcan be an aromatic C₆₋₂₄ monocyclic or polycyclic moiety optionallysubstituted with 1 to 6 C₁₋₈ alkyl groups, 1 to 8 halogen atoms, or acombination thereof, provided that the valence of Z is not exceeded.Exemplary groups Z include groups derived from a dihydroxy compound offormula (3). A specific example of a group Z is a divalent group offormula (19)

wherein Q is —O—, —S—, —C(O)—, —SO₂—, —SO—, and —C_(y)H_(2y)— and ahalogenated derivative thereof (including a perfluoroalkylene group)wherein y is an integer from 1 to 5. In a specific embodiment Z isderived from bisphenol A wherein Q is 2,2-isopropylidene.

More specifically, the first polymer comprises blocks of 10 to 1,000 or10 to 500 structural units of formula (17) wherein R is a divalent groupof formula (19) wherein Q¹ is —C_(y)H_(2y)— wherein y is an integer from1 to 5 or a halogenated derivative thereof, and Z is a group of formula(19). In a specific embodiment, R is m-phenylene, p-arylenediphenylsulfone, or a combination thereof, and Z is2,2-(4-phenylene)isopropylidene.

As is known, polyetherimides can be obtained by polymerization of anaromatic bisanhydride of the formula (20):

wherein Z is as described in formula (17), with a diamine of the formula(21):

H₂N—R—NH₂   (21)

wherein R is as described in formula (17). Illustrative examples of thearomatic bisanhydrides (20) include3,3-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride;4,4′-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride;4,4′-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride;4,4′-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride;4,4′-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride;2,2-bis[4-(2,3-dicarboxyphenoxy)phenyl]propane dianhydride;4,4′-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride;4,4′-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride;4,4′-bis(2,3-dicarboxyphenoxy)benzophenone dianhydride;4,4′-bis(2,3-dicarboxyphenoxy)diphenyl sulfone dianhydride;4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl-2,2-propanedianhydride; 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenylether dianhydride;4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl sulfidedianhydride; 4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)benzophenone dianhydride and4-(2,3-dicarboxyphenoxy)-4′-(3,4-dicarboxyphenoxy)diphenyl sulfonedianhydride. Combinations comprising at least one of the foregoingaromatic bisanhydrides (20) can be used.

Illustrative examples of diamines (21) include ethylenediamine,propylenediamine, trimethylenediamine, diethylenetriamine,triethylenetetramine, hexamethylenediamine, heptamethylenediamine,octamethylenediamine, nonamethylenediamine, decamethylenediamine,1,12-dodecanediamine, 1,18-octadecanediamine,3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine,4-methylnonamethylenediamine, 5-methylnonamethylenediamine,2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine,2,2-dimethylpropylenediamine, N-methyl-bis (3-aminopropyl) amine,3-methoxyhexamethylenediamine, 1,2-bis(3-aminopropoxy) ethane,bis(3-aminopropyl) sulfide, 1,4-cyclohexanediamine,bis-(4-aminocyclohexyl) methane, m-phenylenediamine, p-phenylenediamine,2,4-diaminotoluene, 2,6-diaminotoluene, m-xylylenediamine,p-xylylenediamine, 2-methyl-4,6-diethyl-1,3-phenylene-diamine,5-methyl-4,6-diethyl-1,3-phenylene-diamine, benzidine,3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, 1,5-diaminonaphthalene,bis(4-aminophenyl) methane, bis(2-chloro-4-amino-3,5-diethylphenyl)methane, bis(4-aminophenyl) propane,2,4-bis(amino-t-butyl) toluene, bis(p-amino-t-butylphenyl)ether,bis(p-methyl-o-aminophenyl) benzene, bis(p-methyl-o-aminopentyl)benzene,1, 3-diamino-4-isopropylbenzene, bis(4-aminophenyl)sulfide,bis(4-aminophenyl)sulfone, bis(4-aminophenyl)ether and1,3-bis(3-aminopropyl)tetramethyldisiloxane. Combinations comprising atleast one of the foregoing aromatic bisanhydrides can be used. Aromaticdiamines are often used, especially m- and p-phenylenediamine, sulfonyldianiline and combinations thereof

The poly (siloxane-etherimide)s can be formed by polymerization of anaromatic bisanhydride (20) and a diamine component comprising an organicdiamine (21) or mixture of diamines (21), and a polysiloxane diamine offormula (22):

wherein R and E are as described in formula (9), and R⁴ is eachindependently a C₂-C₂₀ hydrocarbon, in particular a C₂-C₂₀ arylene,alkylene, or arylenealkylene group. In an embodiment R⁴ is a C₂-C₂₀alkyl group, specifically a C₂-C₂₀ alkyl group such as propylene, and Ehas an average value of 5 to 100, 5 to 75, 5 to 60, 5 to 15, or 15 to40. Procedures for making the polysiloxane diamines of formula (22) arewell known in the art. For example, an aminoorganotetraorganodisiloxanecan be equilibrated with an octaorganocyclotetrasiloxane, such asoctamethylcyclotetrasiloxane, to increase the block length of thepolydiorganosiloxane.

In some poly(siloxane-etherimide)s the diamine component can contain 20to 50 mole percent (mol %), or 25 to 40 mol % of polysiloxane diamine(22) and about 50 to 80 mol %, or 60 to 75 mol % of diamine (21), forexample as described in U.S. Pat. No. 4,404,350. The diamine componentscan be physically mixed prior to reaction with the bisanhydride(s), thusforming a substantially random copolymer. Alternatively, block oralternating copolymers can be formed by selective reaction of (21) and(22) with aromatic dianhydrides (20), to make polyimide blocks that aresubsequently reacted together. Thus, the poly(siloxane-imide) copolymercan be a block, random, or graft copolymer.

In an embodiment, the poly(siloxane-etherimide) is made by sequentiallyintercondensing at temperatures in the range of 100° C. to 300° C., thepolysiloxane diamine (22) and the diamine (21) with aromaticbisanhydride (20). A substantially inert organic solvent can be used tofacilitate intercondensation, for example, dipolar aprotic solvents suchas dimethylformamide, N-methyl-2-pyrrolidone, cresol,ortho-dichlorobenzene, and the like. A polymerization catalyst can beused at 0.025 to 1.0% by weight, based on the weight of the reactionmixture, such as an alkali metal aryl phosphinate or alkali metal arylphosphonate, for example, sodium phenylphosphinate.

The sequential intercondensation of the polysiloxane diamine (22) andthe diamine (21) with the aromatic bisanhydride (20) can be achieved ineither a single container or in multiple containers. In the “single pot”procedure, an off stoichiometric amount of either the polysiloxanediamine (22) or the diamine (21), is intercondensed with the aromaticbisanhydride (20) in the presence of an inert organic solvent to producea mixture of polyimide oligomer chain stopped with either intercondenseddiamine or aromatic bisanhydride. An excess of aromatic bisanhydride (2)or diamine (21) corresponding to the chain stopping units also can bepresent. The oligomer can be either a silicone polyimide, or an oligomerof intercondensed aromatic bisanhydride and diamine. There is then addedto the same pot, after the initial period of oligomer formation, theremaining diamine, which can be either the polysiloxane diamine (22) orthe diamine (21) and optionally sufficient aromatic bisanhydride (20) toachieve stoichiometry. There also can be added to the resultingintercondensation mixture, chain stoppers, such a phthalic anhydride ormonofunctional arylamine such as aniline to control the molecular weightof the 55 final silicone polyimide. In the multiple pot procedure,diamine oligomer and polysiloxane diamine oligomer can be intercondensedwith aromatic bisanhydride in separate containers. The multiple potprocedure can achieve satisfactory results in instances where two ormore oligomers are required providing a substantially stoichiometricbalance maintained between total aromatic bisanhydride and diamine.

Oligomer block size can vary depending upon the proportions ofpolysiloxane diamine (22) and the diamine (21) used, per mole ofaromatic bisanhydride (20). For example, for a “three block,” oligomer,a 4/3 ratio can be used, i.e. 4 moles of diamine for 3 moles ofbisanhydride. Reaction can continue until the intercondensation ofanhydride and amine functional groups are achieved and the water ofreaction is completely removed, such as by azeotroping from the reactionmixture.

Examples of such poly(siloxane-etherimide) are described in U.S. Pat.Nos. 4,404,350, 4,808,686 and 4,690,997. In an embodiment, thepoly(siloxane-etherimide) has units of formula (23)

wherein E is as in formula (9), R and Z are as in formula (17), R⁴ is asin formula (22), and n is an integer from 5 to 100.

It is also possible to incorporate polysiloxane units into apoly(siloxane-etherimide) by reaction of diamine (21) with an anhydridecomponent comprising aromatic anhydride (20) and a polysiloxanedianhydride of formula (24), a siloxane dianhydride of formula (25), ora combination thereof:

wherein R and E are as described in structure (9) and each Ar isindependently a C₆-C₃₀ aromatic group. In somepoly(siloxane-etherimide)s the dianhydride component can contain 20 to50 mole percent (mol %), or 25 to 40 mol % of polysiloxane dianhydride(24) and/or (25) and about 50 to 80 mol %, or 60 to 75 mol % ofdianhydride (20), for example as described in U.S. Pat. No. 4,404,350.The anhydride components can be physically mixed prior to reaction withthe diamine(s), thus forming a substantially random copolymer.Alternatively, block or alternating copolymers can be formed byselective reaction of anhydrides (20) and (24) and/or (25) with diamine(21), to make polyimide blocks that are subsequently reacted together.

The relative amount of polysiloxane units and etherimide units in thepoly(siloxane-etherimide) depends on the desired properties, and arecarefully selected using the guidelines provided herein. In particular,as mentioned above, the block or graft poly(siloxane-etherimide)copolymer is selected to have a certain average value of E, and isselected and used in amount effective to provide the desired wt % ofpolysiloxane units in the composition. In an embodiment thepoly(siloxane-etherimide) comprises 10 to 50 wt %, 10 to 40 wt %, or 20to 35 wt % polysiloxane units, based on the total weight of thepoly(siloxane-etherimide).

Other poly(siloxane) copolymers include poly(siloxane-sulfone)copolymers such as poly(siloxane-arylene sulfone)s andpoly(siloxane-arylene ether sulfone)s wherein the first repeating unitsare units of formula (26):

wherein R¹, R², and R³ are each independently a halogen atom, a nitrogroup, a cyano group, a C₁-₁₂ aliphatic radical, C₃-₁₂ cycloaliphaticradical, or a C₃-₁₂ aromatic radical; n, m, q are each independently 0to 4; and W is a C₃-₂₀ cycloaliphatic radical or a C₃-C₂₀ aromaticradical. In an embodiment, the first units (26) contain at least 5 mol %of aromatic ether units of formula (27)

wherein R³ and W are as defined in formula (26). In an embodiment, n, m,and q are each 0 and W is isopropylidene. These poly(siloxane-sulfone)copolymers may be made by reaction of arylene sulfone-containing,arylene ether-containing, or arylene ether sulfone-containing oligomerswith functionalized polysiloxanes to form random or block copolymers.Examples of the poly(siloxane-sulfones and their manufacture, inparticular poly(siloxane-arylene sulfone)s and poly(siloxane-aryleneether sulfone)s, are disclosed in U.S. Pat. Nos. 4,443,581, 3,539,657,3,539,655 and 3,539,655.

The relative amount of polysiloxane units and arylene sulfone units orarylene ether sulfone units in the poly(siloxane-sulfone) copolymersdepends on the desired properties, and are carefully selected using theguidelines provided herein. In particular, the block or graftpoly(siloxane-sulfone) is selected and used in amount effective toprovide the desired wt % of polysiloxane units in the composition. In anembodiment the poly(siloxane-arylene ether sulfone) comprises 10 to 50wt %, 10 to 35 wt %, or 10 to 30 wt % polysiloxane units, based on thetotal weight of the poly(siloxane-arylene ether sulfone).

Other poly(siloxane) copolymers include poly(siloxane-arylene ether)swherein the first repeating units are blocks of units of formula (28):

wherein Z¹ is each independently halogen or C₁-C₁₂ hydrocarbon groupwith the proviso that that the hydrocarbon group is not tertiaryhydrocarbon group; and Z² is each independently hydrogen, halogen, orC₁-C₁₂ hydrocarbon group with the proviso that that the hydrocarbongroup is not tertiary hydrocarbyl. In an embodiment, Z² is hydrogen andZ¹ is methyl.

Poly(siloxane-arylene ether)s and methods for the manufacture ofpoly(siloxane-arylene ether)s have been described in U.S. Pat. No.5,204,438, which is based on the conversion of phenol-siloxane macromersto a silicone polyphenylene ether graft copolymer; and in U.S. Pat. No.4,814,392. U.S. Pat. No. 5,596,048 discloses reaction of a polyaryleneether with a hydroxyaromatic terminated siloxane in the presence of anoxidant.

The relative amount of polysiloxane units and arylene ether units in thepoly(siloxane-arylene ether) depends on the desired properties, and arecarefully selected using the guidelines provided herein. In particular,the block or graft poly(siloxane-arylene ether) copolymer is selectedand used in amount effective to provide the desired wt % of polysiloxaneunits in the composition. In an embodiment the poly(siloxane-aryleneether) comprises 1 to 80 wt %, 5 to 50 wt %, 10 to 35 wt %, or 10 to 30wt % polysiloxane units, based on the total weight of thepoly(siloxane-arylene ether).

Other poly(siloxane) copolymers include poly(siloxane-arylene etherketone)s wherein the first repeating units are units of formula (29):

wherein Z¹ is each independently halogen or C₁-C₁₂ hydrocarbon groupwith the proviso that that the hydrocarbon group is not tertiaryhydrocarbon group; and Z² is each independently hydrogen, halogen, orC₁-C₁₂ hydrocarbon group with the proviso that that the hydrocarbongroup is not tertiary hydrocarbyl. In an embodiment Z² and Z¹ arehydrogen. The arylene ether units and arylene ketone units can bepresent in random order, as blocks (i.e., AABB, or alternating (i.e.,ABAB), or a combination thereof

The relative amount of polysiloxane units and arylene ether ketone unitsin the poly(siloxane-arylene ether ketone) depends on the desiredproperties, and are carefully selected using the guidelines providedherein. In particular, the block or graft poly(siloxane-arylene etherketone) copolymer is selected and used in amount effective to providethe desired wt % of polysiloxane units in the composition. In anembodiment the poly(siloxane-arylene ether ketone) comprises 5 to 50 wt%, 10 to 35 wt %, or 10 to 30 wt % polysiloxane units, based on thetotal weight of the poly(siloxane-arylene ether ketone).

Poly(siloxane-esters), including poly(siloxane-ester-carbonate)copolymers can be used provided that the ester units are selected so asto not significantly adversely affect the desired properties of thepoly(siloxane) copolymer compositions, in particular low smoke densityand low heat release, as well as other properties such as stability toUV light. For example, aromatic ester units can diminish color stabilityof the poly(siloxane) copolymer compositions during processing and whenexposed to UV light. Aromatic ester units can also decrease the meltflow of the polycarbonate composition. On the other hand, the presenceof aliphatic ester units can diminish the heat release values. In anembodiment the poly(siloxane-esters), includingpoly(siloxane-ester-carbonate) copolymers comprise 10 to 50 wt %, 10 to35 wt %, or 10 to 30 wt % polysiloxane units

The first repeating units in the poly(siloxane-esters) orpoly(siloxane-ester-carbonate)s further contain, in addition to thesiloxane blocks of formula (9), repeating units of formula (29):

wherein D is a divalent group derived from a dihydroxy compound, and canbe, for example, a C₂₋₁₀ alkylene group, a C₆₋₂₀ alicyclic group, aC₆₋₂₀ aryl, or a polyoxyalkylene group in which the alkylene groupscontain 2 to 6 carbon atoms, specifically 2, 3, or 4 carbon atoms. In anembodiment, D is a C₂₋₃₀ alkylene having a straight chain, branchedchain, or cyclic (including polycyclic) structure. In anotherembodiment, D is derived from an aromatic dihydroxy compound of formula(3), an aromatic dihydroxy compound of formula (8), or a combinationthereof T in formula (29) is a divalent group derived from adicarboxylic acid, and can be, for example, a C₂₋₁₀ alkylene group, aC₆₋₂₀ alicyclic group, a C₆₋₂₀ alkyl aromatic group, or a C₆₋₂₀ aromaticgroup. Examples of aromatic dicarboxylic acids that can be used toprepare the polyester units include isophthalic or terephthalic acid,1,2-di(p-carboxyphenyl)ethane, 4,4′-dicarboxydiphenyl ether,4,4′-bisbenzoic acid, and combinations comprising at least one of theforegoing acids. Acids containing fused rings can also be present, suchas in 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acids. Specificdicarboxylic acids are terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, cyclohexane dicarboxylic acid, or combinationscomprising at least one of the foregoing. A specific dicarboxylic acidcomprises a combination of isophthalic acid and terephthalic acidwherein the weight ratio of isophthalic acid to terephthalic acid is100:0 to 0:100, or 99:1 to 1:99, or 91:9 to 2:98.

In another specific embodiment, D is a C₂₋₆ alkylene and T isp-phenylene, m-phenylene, naphthalene, a divalent cycloaliphatic group,or a combination comprising at least one of the foregoing.Alternatively, the ester unit can be an arylate ester unit derived fromthe reaction of an aromatic dihydroxy compound of formula (8) (e.g.,resorcinol) with a combination of isophthalic and terephthalic diacids(or derivatives thereof). In another specific embodiment, the ester unitis derived from the reaction of bisphenol A with a combination ofisophthalic acid and terephthalic acid. A specificpoly(siloxane-ester-carbonate) comprises siloxane blocks (9), esterunits derived from resorcinol and isophthalic and/or terephthalicdiacids, and carbonate units (1) derived from resorcinol, bisphenol A,or a combination of resorcinol and bisphenol A in a molar ratio ofresorcinol carbonate units to bisphenol A carbonate units of 1:99 to99:1, specifically 20:80 to 80:20. The molar ratio of ester units tocarbonate units in these copolymers can vary broadly, for example 1:99to 99:1, specifically 10:90 to 90:10, more specifically 25:75 to 75:25,depending on the desired properties of the final composition.Poly(siloxane-ester-carbonate)s of this type can include siloxane blocks(9), and blocks comprising 50 to 99 mol % arylate ester units (e.g.,resorcinol ester units) and 1 to 50 mol % aromatic carbonate unitsincluding resorcinol carbonate units and optionally bisphenol Acarbonate units. Such copolymers are described in U.S. Pat. No.7,605,221.

Any of the foregoing poly(siloxane) copolymers can have an Mw of 5,000to 250,000, specifically 10,000 to 200,000 grams per mole (Daltons),even more specifically 15,000 to 100,000 Daltons, as measured by gelpermeation chromatography (GPC), using a crosslinkedstyrene-divinylbenzene column and calibrated to polycarbonatereferences. GPC samples are prepared at a concentration of 1 mg/ml, andare eluted at a flow rate of 1.5 ml/min.

Melt volume flow rate (often abbreviated “MVR”) measures the rate ofextrusion of a poly(siloxane) copolymer through an orifice at aprescribed temperature and load. The foregoing poly(siloxane) copolymerscan have an MVR, measured at 300° C. under a load of 1.2 kg, of 0.1 to200 cubic centimeters per 10 minutes (cm³/10 min), specifically 1 to 100cm³/10 min.

In some embodiments a combination of two or more differentpoly(siloxane) copolymers are used to obtain the desired properties. Thepoly(siloxane) copolymers can differ in one or more of a property (e.g.,polydispersity or molecular weight) or a structural feature (e.g., thevalue of E, the number of blocks of E, or the identity of the firstrepeating unit). For example, a poly(siloxane-carbonate) having arelatively lower weight percent (e.g., 3 to 10 wt %, or 6 wt %) ofrelatively longer length (E having an average value of 30-60) canprovide a composition of lower colorability, whereas apoly(siloxane-carbonate) having a relatively higher weight percent ofsiloxane units (e.g., 15 to 25 wt %, or 20 wt %) of the same lengthsiloxane units, can provide better impact properties. Use of acombination of these two poly(siloxane-carbonate)s can provide acomposition having both good colorability and impact properties.Similarly, a poly(siloxane-carbonate) can be used with apoly(siloxane-etherimide) to improve impact.

The first polymer, i.e., the poly(siloxane) copolymer, is used with asecond brominated polymer, wherein the type and amount of the brominatedpolymer is selected so as to provide at least 7.8 wt.% bromine to thecomposition as described above. As used herein, a “brominated polymer”is inclusive of homopolymers and copolymers, and includes moleculeshaving at least 2, at least 5, at least 10, or at least 20 repeat unitswith bromine substitution, and an Mw of at least 1,000 Daltons, forexample 1,000 to 50,000 Daltons.

In certain embodiments, the second polymer is a specific brominatedpolycarbonate, i.e., a polycarbonate containing brominated carbonateunits derived from 2,2′,6,6′-tetrabromo-4,4′-isopropylidenediphenol(TBBPA) and carbonate units derived from at least one dihydroxy aromaticcompound that is not TBBPA. The dihydroxy aromatic compound can be oneof formula (5), (6), (7), (8), (9), or (10). In a specific embodimentthe dihydroxy aromatic compound is of formula (5), more specificallydihydroxy aromatic compound (5) containing no additional halogen atoms.In an embodiment, the dihydroxy aromatic compound is Bisphenol A.

The relative ratio of TBBPA to the dihydroxy aromatic compound used tomanufacture the TBBPA copolymer will depend in some embodiments on theamount of the TBBPA copolymer used and the amount of bromine desired inthe polycarbonate composition. In an embodiment, the TBBPA copolymer ismanufactured from a composition having 30 to 70 wt % of TBBPA and 30 to70 wt % of the dihydroxy aromatic compound, specifically Bisphenol A, orspecifically 45 to 55 wt % of TBBPA and 45 to 55 wt % of the dihydroxyaromatic compound, specifically bisphenol A. In an embodiment, no othermonomers are present in the TBBPA copolymer.

Combinations of different TBBPA copolymers can be used. Specifically, aTBBPA copolymer can be used having phenol endcaps. Also specifically, aTBBPA carbonate can be used having 2,4,6-tribromophenol endcaps can beused.

The TBBPA copolymers can have an Mw from 18,000 to 30,000 Daltons,specifically 20,000 to 30,000 Daltons as measured by gel permeationchromatography (GPC) using polycarbonate standards.

Alternatively, the poly(siloxane) copolymer is used with a brominatedoligomer. Thus, instead of a TBBPA copolymer as the second polymer incertain embodiments, a brominated oligomer having an Mw of 18,000Daltons or less is used. The term “brominated oligomer” is used hereinfor convenience to identify a brominated compound comprising at leasttwo repeat units with bromine substitution, and having an Mw of lessthan 18,000 Daltons. The brominated oligomer can have an Mw of 1000 to18,000 Daltons, specifically 2,000 to 15,000 Daltons, and morespecifically 3,000 to 12,000 Daltons.

In certain embodiments the brominated oligomer has a bromine content of40 to 60 wt %, specifically 45 to 55 wt %, more specifically 50 to 55 wt%. The specific brominated oligomer and the amount of brominatedoligomer are selected to provide at least 7.8 wt % bromine, specifically7.8 to 14 wt % bromine, more specifically 8 to 12 wt % bromine, eachbased on the total weight of first polymer, the brominated oligomer, andthe optional additional polycarbonate.

The brominated oligomer can be a brominated polycarbonate oligomerderived from brominated aromatic dihydroxy compounds (e.g., brominatedcompounds of formula (1)) and a carbonate precursor, or from acombination of brominated and non-brominated aromatic dihydroxycompounds, e.g., of formula (1), and a carbonate precursor. Brominatedpolycarbonate oligomers are disclosed, for example, in U.S. Pat. No.4,923,933, U.S. Pat. No. 4,170,711, and U.S. Pat. No. 3,929,908.Examples of brominated aromatic dihydroxy compounds include2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane,bis(3,5-dibromo-4-hydroxyphenyl)menthanone, and2,2′,6,6′-tetramethyl-3,3′,5,5′-tetrabromo-4,4′-biphenol. Examples ofnon-brominated aromatic dihydroxy compounds for copolymerization withthe brominated aromatic dihydroxy compounds include bisphenol A,bis(4-hydroxyphenyl)methane, 2, 2-bis(4-hydroxy-3-methylphenyl)propane,4,4-bis(4-hydroxyphenyl)heptane, and(3,3′-dichloro-4,4′-dihydroxydiphenyl)methane. Combinations of two ormore different brominated and non-brominated aromatic dihydroxycompounds can be used. If a combination of aromatic dihydroxy compoundsis used, then the combinations can contain 25 to 55 mole percent of thebrominated aromatic dihydroxy compounds and 75 to 65 mole percent of anon-brominated dihydric phenol. Branched brominated polycarbonateoligomers can also be used, as can compositions of a linear brominatedpolycarbonate oligomer and a branched brominated polycarbonate oligomer.Combinations of different brominated copolycarbonate oligomers can beused. Various endcaps can be present, for example polycarbonates havingphenol endcaps or 2,4,6-tribromophenol endcaps can be used.

Other types of brominated oligomers can be used, for example brominatedepoxy oligomers. Examples of brominated epoxy oligomers include thosederived from Bisphenol A, hydrogenated Bisphenol A, Bisphenol-F,Bisphenol-S, novolak epoxies, phenol novolac epoxies, cresol novolacepoxies, N-glycidyl epoxies, glyoxal epoxies dicyclopentadiene phenolicepoxies, silicone-modified epoxies, and epsilon-caprolactone modifiedepoxies. Combinations of different brominated epoxy oligomers can beused. Specifically, a tetrabromobisphenol A epoxy be used, having2,4,6-tribromophenol endcaps. An epoxy equivalent weight of 200 to 3000can be used.

In some embodiments a combination of two or more different brominatedpolymers are used to obtain the desired properties. The brominatedpolymers can differ in one or more of a property (e.g., polydispersityor molecular weight) or a structural feature (e.g., the identity of therepeating units, the presence of copolymer units, or the amount ofbromine in the polymer). For example, two different TBBPA copolymers canbe used, or a combination of a TBBPA copolymer and a brominated epoxyoligomer. Of course, two or more different poly(siloxane) copolymers canbe used with two or more different brominated polymers.

The poly(siloxane) copolymer compositions can further optionallycomprise one or more polymers additional to the poly(siloxane) copolymerand the brominated polymer, which can be referred to herein as “one ormore third polymers” for convenience. The one or more third polymers canbe homopolymers or copolymers and can have repeating units that are thesame or different from first repeating units of the poly(siloxane)copolymer. The one or more third polymers can comprise different typesof repeating units, provided that the type and amount of repeating unitsdoes not significantly adversely affect the desired properties of thecompositions, in particular low smoke density and low heat release. Theone or more third polymers can comprise carbonate units (1), imideunits, etherimide units (17), arylene ether sulfone units (26), aryleneether units (28), ester units (29), or a combination of units comprisingat least one of the foregoing. However, in an embodiment, the one ormore third polymers do not contain either polysiloxane units or bromine

The one or more third polymers can have an Mw, for example, of 5,000 to500,000 Daltons, specifically 10,000 to 250,000 Daltons, or 10,000 to100,000 Daltons , as measured by gel permeation chromatography (GPC),using a crosslinked styrene-divinylbenzene column and calibrated topolycarbonate references. GPC samples are prepared at a concentration of1 mg/ml, and are eluted at a flow rate of 1.5 ml/min. The one or morethird polymers can have an MVR, measured at 300° C. under a load of 1.2kg, of 0.1 to 200 cubic centimeters per 10 minutes (cm³/10 min),specifically 1 to 100 cm³/10 min.

The one or more third polymers is selected and used in an amount toprovide the desired characteristics to the compositions. The amount ofthe one or more third polycarbonates can be 0 to 85 wt %, 1 to 80 wt %,5 to 75 wt %, 8 to 60 wt %, 20 to 50 wt %, or 30 to 40 wt %, based onthe total weight of the first polymer, the second polymer, and the oneor more third polymers. In a specific embodiment the he third polymer ispresent in an amount of 8 to 50 wt %, the polysiloxane unit is presentin an amount of 1.5 to 3.5 wt %, and the bromine is present in an amountof 7.8 to 13 wt %, each based on the sum of the wt % of the first,second, and third polymers.

In a specific embodiment, in the polycarbonate compositions comprising apoly(siloxane-carbonate) and the TBBPA copolymer, an optional thirdpolycarbonate can be present that is not same as the firstpoly(siloxane-carbonate) or the TBBPA copolymer. Specifically in certainembodiments, the one or more third polymers do not contain eitherpolysiloxane units or bromine In the alternative polycarbonatecompositions comprising the poly(siloxane-carbonate) and the brominatedoligomer, an additional polycarbonate that is not the same as the firstpoly(siloxane) or the brominated oligomer is present. Specifically, theadditional polycarbonate does not contain polysiloxane units or bromine.

When the optional one or more third polymer is a polycarbonate, thepolymer comprises units of formula (1) as described above, specificallywherein R¹ is derived from the dihydroxy aromatic compound (2) (3), (8),or a combination thereof, and more the specifically dihydroxy aromaticcompound (3) containing no additional halogen atoms. In an embodiment,at least 60%, at least 80%, or at least 90% of the R¹ units arebisphenol A units. In an embodiment, the optional one or more thirdpolymer (including the additional polycarbonate) is a homopolymer withbisphenol A carbonate units.

It is also possible for the one or more third polycarbonates oradditional polycarbonates to contain units other than polycarbonateunits, for example ester units (29), provided that the ester units areselected so as to not significantly adversely affect the desiredproperties of the poly(siloxane) copolymer compositions as describedabove. In an embodiment, the ester units are arylate ester unit derivedfrom the reaction of an aromatic dihydroxy compound of formula (8)(e.g., resorcinol) with a combination of isophthalic and terephthalicdiacids (or derivatives thereof). In another specific embodiment, theester unit is derived from the reaction of bisphenol A with acombination of isophthalic acid and terephthalic acid. A specificpoly(ester-carbonate) comprises ester units derived from resorcinol andisophthalic and/or terephthalic diacids, and carbonate units (1) derivedfrom resorcinol, bisphenol A, or a combination of resorcinol andbisphenol A in a molar ratio of resorcinol carbonate units to bisphenolA carbonate units of 1:99 to 99:1, specifically 20:80 to 80:20. Themolar ratio of ester units to carbonate units in these copolymers canvary broadly, for example 1:99 to 99:1, specifically 10:90 to 90:10,more specifically 25:75 to 75:25, depending on the desired properties ofthe final composition.

In addition to the poly(siloxane) copolymer brominated polymer, and oneor more optional third polymers, the poly(siloxane) copolymercompositions can include various additives ordinarily incorporated intoflame retardant compositions having low smoke density and low heatrelease, with the proviso that the additive(s) are selected so as to notadversely affect the desired properties of the poly(siloxane) copolymercomposition significantly, in particular low smoke density low heatrelease. Such additives can be mixed at a suitable time during themixing of the components for forming the composition. Exemplaryadditives include fillers, reinforcing agents, antioxidants, heatstabilizers, light stabilizers, ultraviolet (UV) light stabilizers,plasticizers, lubricants, mold release agents, antistatic agents,colorants such as such as titanium dioxide, carbon black, and organicdyes, surface effect additives, radiation stabilizers, additional flameretardants, and anti-drip agents. A combination of additives can beused. In general, the additives are used in the amounts generally knownto be effective. The total amount of additives (other than any filler orreinforcing agents) is generally 0.01 to 25 parts per parts per hundredparts by weight of the combination of the first, second, and optionalone or more third polymers (PHR).

In an advantageous embodiment, it has been found that certain importantadditives can be used without adversely affecting the heat release andlow smoke properties of the poly(siloxane) copolymer compositionssignificantly, in particular UV stabilizers, heat stabilizers (includingphosphites), other flame retardants (such as Rimar salts) and certainpigments. The use of pigments such as titanium dioxide produces whitecompositions, which are commercially desirable. Pigments such astitanium dioxide (or other mineral fillers) can be present in thepoly(siloxane) copolymer compositions in amounts of 0 to 12 PHR, 0.1 to9 PHR, 0.5 to 5 PHR, or 0.5 to 3 PHR.

Exemplary antioxidant additives include organophosphites such astris(nonyl phenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite,bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite; alkylated monophenols or polyphenols;alkylated reaction products of polyphenols with dienes, such astetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane;butylated reaction products of para-cresol or dicyclopentadiene;alkylated hydroquinones; hydroxylated thiodiphenyl ethers;alkylidene-bisphenols; benzyl compounds; esters ofbeta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with monohydricor polyhydric alcohols; esters ofbeta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid withmonohydric or polyhydric alcohols; esters of thioalkyl or thioarylcompounds such as distearylthiopropionate, dilaurylthiopropionate,ditridecylthiodipropionate,octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate;amides of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid, orcombinations comprising at least one of the foregoing antioxidants.Antioxidants are used in amounts of 0.01 to 0.1 PHR.

Exemplary heat stabilizer additives include organophosphites such astriphenyl phosphite, tris-(2,6-dimethylphenyl)phosphite, tris-(mixedmono-and di-nonylphenyl)phosphite; phosphonates such as dimethylbenzenephosphonate, phosphates such as trimethyl phosphate , or combinationscomprising at least one of the foregoing heat stabilizers. Heatstabilizers are used in amounts of 0.01 to 0.1 PHR.

Light stabilizers and/or ultraviolet light (UV) absorbing additives canalso be used. Exemplary light stabilizer additives includebenzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole,2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole and 2-hydroxy-4-n-octoxybenzophenone , or combinations comprising at least one of the foregoinglight stabilizers. Light stabilizers are used in amounts of 0.01 to 5PHR.

Exemplary UV absorbing additives include hydroxybenzophenones;hydroxybenzotriazoles; hydroxybenzotriazines; cyanoacrylates;oxanilides; benzoxazinones;2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol(CYASORB®5411); 2-hydroxy-4-n-octyloxybenzophenone (CYASORB® 531);2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)-phenol(CYASORB® 1164); 2,2′-(1,4-phenylene)bis(4H-3,1 -benzoxazin-4-one)(CYASORB® UV-3638); 1,3 -bis[(2-cyano-3,3 -diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane (UVINUL® 3030);2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one);1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane;nano-size inorganic materials such as titanium oxide, cerium oxide, andzinc oxide, all with particle size less than or equal to 100nanometers;, or combinations comprising at least one of the foregoing UVabsorbers. UV absorbers are used in amounts of 0.01 to 5 PHR.

Plasticizers, lubricants, and/or mold release agents can also be used.There is considerable overlap among these types of materials, whichinclude phthalic acid esters such asdioctyl-4,5-epoxy-hexahydrophthalate;tris-(octoxycarbonylethyl)isocyanurate; tristearin; di- orpolyfunctional aromatic phosphates such as resorcinol tetraphenyldiphosphate (RDP), the bis(diphenyl) phosphate of hydroquinone and thebis(diphenyl) phosphate of bisphenol A; poly-alpha-olefins; epoxidizedsoybean oil; silicones, including silicone oils; esters, for example,fatty acid esters such as alkyl stearyl esters, e.g., methyl stearate,stearyl stearate, pentaerythritol tetrastearate, and the like;combinations of methyl stearate and hydrophilic and hydrophobic nonionicsurfactants comprising polyethylene glycol polymers, polypropyleneglycol polymers, poly(ethylene glycol-co-propylene glycol) copolymers,or a combination comprising at least one of the foregoing glycolpolymers, e.g., methyl stearate and polyethylene-polypropylene glycolcopolymer in a solvent; waxes such as beeswax, montan wax, and paraffinwax. Such materials are used in amounts of 0.1 to 1 PHR.

Additional monomeric flame retardants include organic compounds thatinclude phosphorus, bromine, and/or chlorine. Non-brominated andnon-chlorinated phosphorus-containing flame retardants can be added forcertain applications, for example organic compounds containingphosphorus-nitrogen bonds.

Inorganic flame retardants can also be used, for example salts of C₁₋₁₆alkyl sulfonate salts such as potassium perfluorobutane sulfonate (Rimarsalt), potassium perfluorooctane sulfonate, tetraethylammoniumperfluorohexane sulfonate, and potassium diphenylsulfone sulfonate;salts such as Na₂CO₃, K₂CO₃, MgCO₃, CaCO₃, and BaCO₃, or fluoro-anioncomplexes such as Li₃AlF₆, BaSiF₆, KBF₄, K₃AlF₆, KAlF₄, K₂SiF₆, and/orNa₃AlF₆. When present, inorganic flame retardant salts are present inamounts of 0.01 to 10 PHR, more specifically 0.02 to 1 PHR.

Anti-drip agents in most embodiments are not used in the poly(siloxane)copolymer compositions. Anti-drip agents include a fibril-forming ornon-fibril forming fluoropolymer such as polytetrafluoroethylene (PTFE).The anti-drip agent can be encapsulated by a rigid copolymer, forexample styrene-acrylonitrile copolymer (SAN). PTFE encapsulated in SANis known as TSAN. Antidrip agents are substantially absent or completelyabsent from the poly(siloxane) copolymer compositions in someembodiments.

Methods for forming the poly(siloxane) copolymer compositions can vary.In an embodiment, the poly(siloxane) copolymer, brominated polymer, andoptional one or more third polymers are combined (e.g., blended) withany additives (e.g., a mold release agent) such as in a screw-typeextruder. The poly(siloxane) copolymer, brominated polymer, optional oneor more third polymers and any additives can be combined in any order,and in form, for example, powder, granular, filamentous, as amasterbatch, and the like. The composition can then be foamed, extrudedinto a sheet or optionally pelletized. Methods of foaming athermoplastic composition using frothing or physical or chemical blowingagents are known and can be used. The pellets can be used for moldinginto articles, foaming, or they can be used in forming a sheet of theflame retardant poly(siloxane) copolymer composition. In someembodiments, the composition can be extruded (or co-extruded with acoating or other layer) in the form of a sheet and/or can be processedthrough calendaring rolls to form the desired sheet.

As discussed above, the poly(siloxane) copolymer compositions areformulated to meet strict flammability requirements. The poly(siloxane)copolymer compositions have an E662 smoke test D_(max) value of lessthan 200 when tested at a thickness of 1.6 mm, and in some embodimentscan further have a value of less than 150, less than 100, less than 80,or 70 to 72. The poly(siloxane) copolymer compositions can have an E662smoke test D_(max) value of 70 to 200, 70 to 150, 70 to 100, or 70 to80.

The poly(siloxane) copolymer compositions further have an OSU integrated2 minute heat release test value of less than 65 kW-min/m² and a peakheat release rate of less than 65 kW/m² as measured using the method ofFAR F25.4, in accordance with Federal Aviation Regulation FAR 25.853(d). In some embodiments the poly(siloxane) copolymer compositions canhave an OSU integrated 2 minute heat release test value of less than 55kW-min/m² and a peak heat release rate of less than 55 kW/m² as measuredusing the method of FAR F25.4, in accordance with Federal AviationRegulation FAR 25.853 (d).

The poly(siloxane) copolymer compositions can further be formulated tohave a haze less than 3% and a transmission greater than 85%, eachmeasured using the color space CIE1931 (Illuminant C and a 2° observer)or according to ASTM D 1003 (2007) using illuminant C at a 0.062 inch(1.5 mm) thickness. In some embodiments, the poly(siloxane) copolymercompositions can be formulated such that an article molded from thecomposition has all three of a haze less of than 15% and a transmissionof greater than 75%, each measured using the color space CIE1931(Illuminant C and a 2° observer) or according to ASTM D 1003 (2007)using illuminant C at a 0.125 inch (3 2 mm) thickness, and a roomtemperature notched Izod impact of greater than 500 J/m as measuredaccording to ASTM D 256-10 at a 0.125 inch (3.2 mm) thickness.

Density (or specific gravity) is a critical factor in aircraftcomponents, and the poly(siloxane) copolymer compositions can beformulated to have lower densities, in particular a density of 1.31 g/ccor less, 1.30 g/cc or less, or 1.29 g/cc or less. Such densities cangenerally be obtained when the amount of bromine is less than 15 wt %,13 wt %, 12 wt %, 11 wt %, 10 wt %, 9 wt %, 8 wt %, or 7.8 wt %, eachbased on the total weight of the first polymer, second polymer, andoptional one or more third polymers.

The poly(siloxane-carbonate) compositions can further be formulated tohave a hydrogen to carbon ratio of 0.81:1 to 0.88:1.

The compositions can further have good melt viscosities, which aidsprocessing. The poly(siloxane) copolymer compositions can have a meltvolume flow rate (MVR, cubic centimeter per 10 minutes (cc/10 min),according to ASTM D 1238) of less than 20, less than 19, less than 18,less than 17, less than 16, less than 15, or less than 12, measured at300° C./1.2 Kg at 360 second dwell.

In a specific embodiment, the polycarbonate compositions (i.e.,compositions containing poly(siloxane-carbonate), brominated polymer,and one or more optional third polycarbonates) are formulated to meetstrict flammability requirements. The compositions have an E662 smoketest D_(max) value of less than 200 when tested at a thickness of 1.6mm, and in some embodiments can further have a value of less than 150,less than 100, less than 80, or 70 to 72.

The polycarbonate compositions can further have an OSU integrated 2minute heat release test value of less than 65 kW-min/m² and a peak heatrelease rate of less than 65 kW/m² as measured using the method of FARF25.4, in accordance with Federal Aviation Regulation FAR 25.853 (d). Insome embodiments the polycarbonate compositions can have an OSUintegrated 2 minute heat release test value of less than 55 kW-min/m²and a peak heat release rate of less than 55 kW/m² as measured using themethod of FAR F25.4, in accordance with Federal Aviation Regulation FAR25.853 (d).

The polycarbonate compositions can further have excellent impactstrength, particularly when the average value of E is higher, i.e.,25-200, 25-100, or 25 to 50. Such compositions often have highersiloxane levels, i.e., at least 2.0 wt %, specifically 2.0 to 8 wt %,2.0 to 5 wt %, 2.0 to 4 wt %, or 2.0 to 3.5 wt %, each based on thetotal weight of the poly(siloxane-carbonate), brominated copolymer, andoptional one or more third polymers, or based on the total weight of thefirst polymer, the brominated oligomer, and the optional additionalpolycarbonate. An article molded from the polycarbonate compositions canhave a notched Izod impact of greater than 500 Pm as measured accordingto ASTM D 256-10 at a 0.125 inch (3.2 mm) thickness. In some embodimentsthe articles have 80% or 100% ductility.

In some applications, it can be desirable to have a transparent article.Haze values, as measured using the color space C1E1931 (Illuminant C anda 2° observer), or by ANSI/ASTM D1003 (2007), Procedure A, illuminant C,can be a useful determination of the optical properties of thetransparent flame retardant polycarbonate sheet. The lower the hazelevels, the better the transparency of the finished sheet. In anembodiment, haze levels for an article comprising the polycarbonatecomposition, when measured at a thickness of 1.5 millimeters (mm), canbe less than 10%, specifically 0 to 10%, 0.5 to 10%, and morespecifically 1 to 10%, and transparency as measured by % transmissioncan be 70% or greater, specifically 80% or greater, greater than orequal to 75%, more specifically, greater than or equal to 90%, asmeasured using the color space CIE1931 (Illuminant C and a 2° observer),or in accordance with ASTM D1003-07, Procedure A, illuminant C. Thesevalues can be obtained even when average value of E in thepoly(siloxane-carbonate) is higher, i.e., 25 to 200, 25 to 100, or 25 to50. Such compositions often have higher siloxane levels, i.e., at least2.0 wt %, specifically 2.0 to 8 wt %, 2.0 to 5 wt %, 2.0 to 4 wt %, or2.0 to 3.5 wt %, based on the total weight of the polymers (andoligomers, if present) in the polycarbonate compositions. The TBBPAcopolymer can be present in an amount from 35 to 50 wt %, and thebromine can be present in an amount of at least 7.8 wt %, specifically 8to 25 wt %, more specifically 8 to 13 wt %, or 10 to 13 wt %, each basedon the total weight of the poly(siloxane-carbonate), TBBPA copolymer,and optional one or more third polymers. The bromine-containing oligomercan be present in an amount from 15 to 30 wt %, and the bromine can bepresent in an amount greater than 8 wt %, specifically 8 to 25 wt %,more specifically 8 to 13 wt %, based on the total weight of thepoly(siloxane-carbonate), the brominated oligomer, and the additionalpolycarbonate.

In another embodiment, even greater transparency can be obtained whenthe poly(siloxane-carbonate) has an average value of E that is lower,i.e., 5 to 75, 5 to 50, or 5 to 15, specifically 7 to 13, or 8 to 12.Such compositions further have at least 30 wt %, specifically 30 to 80wt %, or 30 to 60 wt % of the poly(siloxane-carbonate), at least 20 wt%, specifically 20 to 70 wt %, or 20 to 65 wt % of the TBBPA copolymer,and 0 to 50 wt %, specifically 0 to 30 wt %, or 5 to 20 wt % of theoptional third copolymer; lower siloxane levels, i.e., at least 0.3 wt%, specifically 0.3 to 2 wt %, 0.3 to 1 wt %, 0.3 to 0.8 wt %; and atleast 5 wt %, specifically 5 to 20 wt % bromine, 5 to 10 wt %, or 7.8 to13 wt % of bromine, each based on the total weight of the first polymer,TBBPA copolymer, and optional one or more third polymers.

Density (or specific gravity), is a critical factor in aircraftcomponents, and the polycarbonate compositions can be formulated to havelower densities, in particular a density of 1.31 gram per cubiccentimeter (g/cc) or less, 1.30 g/cc or less, or 1.29 g/cc or less. Suchdensities can generally be obtained when the amount of bromine is lessthan 15 wt %, 13 wt %, 12 wt %, 11 wt %, 10 wt %, 9 wt %, 8 wt %, or 7.8wt %, each based on the total weight of the poly(siloxane-carbonate),TBBPA copolymer, and optional one or more third polymers, or based onthe total weight of the poly(siloxane-carbonate), the brominatedoligomer, and the additional polycarbonate.

The compositions can further have good melt viscosities, which aidsprocessing. The polycarbonate compositions can have a melt volume rate(MVR, cc/10 min., ASTM D 1238) of less than 20, less than 19, less than18, less than 17, less than 16, less than 15, or less than 12, measuredat 300° C./1.2 Kg at 360 second dwell.

As mentioned throughout, the poly(siloxane) copolymer compositions canbe used in a wide variety of applications, particularly those requiringlow smoke and low heat release values. Articles comprising thepoly(siloxane) copolymer compositions can be manufactured by foaming,molding, thermoforming, extruding, or casting the poly(siloxane)copolymer compositions. Thus the poly(siloxane) copolymer compositionscan be used to form a foamed article, a molded article, a thermoformedarticle, an extruded film, an extruded sheet, one or more layers of amulti-layer article, a substrate for a coated article, or a substratefor a metallized article.

Illustrative articles include access panels, access doors, air flowregulators air gaspers, air grilles, arm rests, baggage storage doors,balcony components, cabinet walls, ceiling panels, door pulls, doorhandles, duct housing, enclosures for electronic devices, equipmenthousings, equipment panels, floor panels, food carts, food trays, galleysurfaces, grilles, handles, housings for TVs and displays, light panels,magazine racks, telephone housings, partitions, parts for trolley carts,seat backs, seat components, railing components, seat housings, shelves,side walls, speaker housings, storage compartments, storage housings,toilet seats, tray tables, trays, trim panel, window moldings, windowslides, windows, and the like. The poly(siloxane) copolymer compositionsare particularly useful in train and aircraft, for example a variety ofaircraft compartment interior applications, as well as interiorapplications for other modes of transportation, such as bus, train,subway, marine, and the like. The articles manufactured from thecompositions described herein can thus be a component of an aircraft,train, marine, subway vehicle, or other transportation applications. Ina specific embodiment the articles interior components for aircraft ortrains, including access panels, access doors, air flow regulatorsbaggage storage doors, display panels, display units, door handles, doorpulls, enclosures for electronic devices, food carts, food trays,grilles, handles, magazine racks, seat components, partitions,refrigerator doors, seat backs, side walls, tray tables, trim panels,and the like. The poly(siloxane) copolymer compositions can be formed(e.g., molded) into sheets that can be used for any of the abovementioned components. It is generally noted that the overall size,shape, thickness, optical properties, and the like of the polycarbonatesheet can vary depending upon the desired application.

In some applications, it can be desirable to have a transparent flameretardant article, such as a sheet. With regard to the transparency ofthe sheet, end user specifications (e.g., commercial airlinespecifications) generally specify that the component satisfy aparticular predetermined threshold. Haze values, as measured using thecolor space CIE1931 (Illuminant C and a 2° observer), or by ANSI/ASTMD1003-00, Procedure A, illuminant C, can be a useful determination ofthe optical properties of the transparent flame retardant polycarbonatearticles such as a sheet. The lower the haze levels, the better thetransparency of the finished article.

The transparent poly(siloxane) copolymer compositions have specialutility in applications requiring clarity, for example any of the abovearticles or components can be manufactured using the transparentpolycarbonate compositions disclosed herein. In an embodiment, thetransparent polycarbonate compositions are used for the manufacture ofbalcony components, balusters for stairs and balconies, ceiling panels,covers for life vests, covers for storage bins, dust covers for windows,layers of an electrochromic device, lenses for televisions, electronicdisplays, gauges, or instrument panels, light covers, light diffusers,light tubes and light pipes, mirrors, partitions, railings, refrigeratordoors, shower doors, sink bowls, trolley cart containers, trolley cartside panels, windows, or the like, particularly in aircraft, marinetransports, or trains.

Any of the foregoing articles, but in particular the transparentarticles, can further have a hardcoat disposed on a surface of thearticle to enhance abrasion and scratch resistance, chemical resistance,and the like. Hardcoats are known in the art, and include, for example,various polyacrylates such as hyperbranched polyacrylates, silicones,polyfluoroacrylates, urethane-acrylates, phenolics, perfluorpolyethers,and the like.

The disclosure is further illustrated by the following Examples. Itshould be understood that the non-limiting examples are merely given forthe purpose of illustration. Unless otherwise indicated, parts andpercentages are by weight based upon the total weight of thepoly(siloxane) copolymer, brominated polymer, and optional one or morethird polymers in the poly(siloxane) copolymer compositions. The amountof additives is thus given in parts by weight per hundred parts byweight of the resins (PHR).

EXAMPLES Materials.

The descriptions of the polycarbonates and polycarbonate copolymers usedin the Examples are described in Table 1. Methods for preparing thebrominated polycarbonates and the poly(siloxane-carbonate) copolymersare described after Table 1.

In Table 1, a reference to D10, D30, or D45 means a dimethylsiloxaneblock having an average length of 10.5+/−2.5, with two additionalterminal silicon group (with silicon hydride levels of less than 20 ppm,volatiles of less than 0.4%), 30+/−4 with two additional terminalsilicon groups (with silicon hydride levels of less than 20 ppm,volatiles of less than 0.4%, and D3 and D4 levels of less than 10 and1000 ppm respectively), or 45+/−5 with two additional terminal silicongroups (with silicon hydride levels of less than 20 ppm, volatiles ofless than 0.4%, and D3 and D4 levels of less than 10 and 1000 ppmrespectively.). The values of D and wt % siloxane for the copolymers inTable 1 were as charged to the reactor.

The weight average molecular weights (Mw) of the polymers and copolymersin Table 1 were measured by gel permeation chromatography usingpolycarbonate standards. The endcap was PCP (p-cumyl phenol) or phenol.The percent of siloxane and bromine is weight percent based on theweight of the copolymer.

TABLE 1 Wt % Avg. Siloxane Wt % Acronym Description Mw PDI EndcapSiloxane Length Br TBBPA-BPA TetrabromoBPA/BPA Copolymer 23,660 2.6 PCP— — 26 BC52 Tetrabromo BPA Oligomer 2,638 1.7 Phenol — — 52 SiPC 1 D10siloxane block co-polycarbonate 30,000 — PCP 1 10 — SiPC 1B D10 siloxaneblock co-polycarbonate 22,200 — PCP 1 10 — SiPC 2 D10 siloxane blockco-polycarbonate 23,600 3.0 PCP 5 10 — SiPC 3 D30 siloxane blockco-polycarbonate 23,472 2.2 PCP 6 30 — SiPC 4 D45 siloxane blockco-polycarbonate 23,013 2.2 PCP 6 45 — SiPC 5 D45 siloxane blockco-polycarbonate 29,852 2.6 PCP 20  45 — PC 1 PCP Capped BPAPolycarbonate 21,900 2.5 PCP — — — PC 2 PCP Capped BPA Polycarbonate29,830 2.5 PCP — — —

TBBPA-BPA Copolymer.

A representative reaction description for a 26 wt % brominecopolycarbonate batch is as follows.

To the formulation tank was added dichloromethane (16 L), DI water (12L), bisphenol A (2250 g, 9.9 moles), tetrabromobisphenol A (2250 g, 4.1moles), p-cumylphenol (102 g, 0.48 mole), triethylamine (75 g, 0.74mole) and sodium gluconate (10 g). The mixture was transferred to thebatch reactor. The reactor agitator was started and circulation flow wasset at 80 L/min. Phosgene flow to the reactor was initiated (80 g/minrate). A pH target of 10.0 was maintained throughout the batch by theaddition of 33% aqueous sodium hydroxide. The total phosgene additionamount was 2500 g (25.3 moles). After the phosgene addition wascomplete, a sample from the reactor was obtained and verified to besubstantially free of unreacted monomers and chloroformates. Mw of thereaction sample was determined by GPC (Mw=23660, PDI=2.6). The reactorwas purged with nitrogen then the batch was transferred to thecentrifuge feed tank. To the batch in the feed tank was added dilutiondichloromethane (10 L) then the mixture was purified using a train ofliquid-liquid centrifuges. Centrifuge one removed the brine phase.Centrifuge two removed the catalyst by extracting the polymer solutionwith aqueous hydrochloric acid (pH 1). Centrifuges three through eightsubstantially removed residual ions by extracting the polymer solutionwith DI water. A sample of the polymer solution was tested and verifiedless than 5 ppm each of ionic chloride and residual triethylamine.

The polymer solution was transferred to the precipitation feed tank. Thepolymer was isolated as a white powder by steam precipitation followedby drying in a cone shaped dryer using heated nitrogen (210° F.).Mw=23532. A pressed film of a sample of the polymer was transparent andtough.

SiPC 1 (1D10 Copolymer): A representative reaction description for a 1%siloxane D10 poly(siloxane-carbonate) is as follows. To the formulationtank was added dichloromethane (15 L), DI water (12 L), bisphenol A(4410 g, 19.3 moles), D10 eugenol-capped siloxane (90 g, 0.07 moles),p-cumylphenol (174 g, 0.82 mole), triethylamine (30 g, 0.30 mole) andsodium gluconate (10 g). The mixture was transferred to the batchreactor. The reactor agitator was started and circulation flow was setat 80 L/min Phosgene flow to the reactor was initiated (80 g/min rate).A pH target of 10.0 was maintained throughout the batch by the additionof 33% aqueous sodium hydroxide. The total phosgene addition amount was2300 g (23.3 moles). After the phosgene addition was complete, a samplefrom the reactor was obtained and verified to be substantially free ofunreacted BPA and chloroformates. Mw of the reaction sample wasdetermined by GPC (Mw=22370 Daltons, PDI=2.4). The reactor was purgedwith nitrogen then the batch was transferred to the centrifuge feedtank.

To the batch in the feed tank was added dilution dichloromethane (10 L)then the mixture was purified using a train of liquid-liquidcentrifuges. Centrifuge one removed the brine phase. Centrifuge tworemoved the catalyst by extracting the polymer solution with aqueoushydrochloric acid (pH 1). Centrifuges three through eight substantiallyremoved residual ions by extracting the polymer solution with DI water.A sample of the polymer solution was tested and verified less than 5 ppmeach of ionic chloride and residual triethylamine.

The polymer solution was transferred to the precipitation feed tank. Thepolymer was isolated as a white powder by steam precipitation followedby drying in a cone shaped dryer using heated nitrogen (99° C. (210°F.)).

SiPC 2 (5D10 Copolymer).

A representative reaction description for a 5 wt % siloxane D10poly(siloxane-carbonate) batch is as follows.

To the formulation tank was added dichloromethane (15 L), DI water (12L), bisphenol A (4125 g, 18.1 moles), D10 eugenol capped siloxane (375g, 0.30 moles), p-cumylphenol (166 g, 0.78 mole), triethylamine (30 g,0.30 mole) and sodium gluconate (10 g). The mixture was transferred tothe batch reactor. The reactor agitator was started and circulation flowwas set at 80 L/min. Phosgene flow to the reactor was initiated (80g/min rate). A pH target of 10.0 was maintained throughout the batch bythe addition of 33% aqueous sodium hydroxide. The total phosgeneaddition amount was 2300 g (23.3 moles). After the phosgene addition wascomplete, a sample of the reactor was obtained and verified to besubstantially free of unreacted BPA and chloroformates. Mw of thereaction sample was determined by GPC (Mw=21991 Daltons, PDI=2.6). Thereactor was purged with nitrogen then the batch was transferred to thecentrifuge feed tank.

To the batch in the feed tank was added dilution dichloromethane (10 L)then the mixture was purified using a train of liquid-liquidcentrifuges. Centrifuge one removed the brine phase. Centrifuge tworemoved the catalyst by extracting the polymer solution with aqueoushydrochloric acid (pH 1). Centrifuges three through eight substantiallyremoved residual ions by extracting the polymer solution with DI water.A sample of the polymer solution was tested and verified less than 5 ppmeach of ionic chloride and residual triethylamine.

The polymer solution was transferred to the precipitation feed tank. Thepolymer was isolated as a white powder by steam precipitation followedby drying in a cone shaped dryer using heated nitrogen (210° F.).Mw=21589 Daltons.

SiPC 3 (6D30 Copolymer).

The 6D30 copolymer (6 wt % siloxane D30 poly(siloxane-carbonate)) wasmade in similar fashion to Examples 14 and 15 in U.S. Pat. No. 6,870,013using a D30 eugenol-capped siloxane fluid. The polymer contains about 6wt % siloxane. The Mw is about 23,500 Daltons.

SiPC 4 (6D45 Copolymer).

The 6D45 polymer (6 wt % siloxane D45 poly(siloxane-carbonate)) was madein similar fashion to Examples 14 and 15 in US 6,870,013 using D45eugenol-capped siloxane fluid. The polymer contains about 6% siloxane.The Mw is about 23,000 Daltons.

SiPC 5 (20D45 Copolymer):

The 20D45 polymer (20 wt % siloxane D45 poly(siloxane-carbonate)) wasmade in a like manner to the 5D10 poly(siloxane-carbonate) except that aD45 eugenol-capped siloxane fluid was used. The polymer contains about20% siloxane. The Mw is about 30,000 Daltons.

The additive types and details that were used in the compositions of theExamples are shown in Table 2.

TABLE 2 Component Chemical Name Supplier Grade Phosphite Tris(2,4-di-tert-butylphenyl) phosphite various DF1040 Methylhydrogensiloxane fluid Momentive Performance DF 1040 Materials OPTSOctaphenylcyclotetrasiloxane Shin-Etsu Chemical Co. — D4Octamethyltetrasiloxane Aldrich Chemical Co. — KSS Potassiumdiphenylsulfone sulfonato Arichem LLC KSS Rimar salt Potassiumperfluorobutane sulfonato Lanxess Bayowet C4 STB Sodium trichlorobenzenesulfonato Arichem LLC STB sesquihydrate TSAN SAN encapsulated PTFE SabicInnovative Plastics TSAN TiO₂ Type 1 Titanium dioxide, (organic coating)Kronos Kronos 2233 TiO₂ Type 2 Titanium dioxide, (organic coating)Kronos KRONOS 2450 Phosphorus acid Phosphorus acid solution (0.15%)Tinuvin 1577 2-(4,6-Diphenyl-1,3,5-triazin-2-yl)-5- Ciba SpecialtyCompany Tinuvin 1577 FF hexyloxyphenol Corp. UVA 2342-(2-hydroxy-3,5-di-cumyl)benzotriazole Ciba Specialty Company Tinuvin234 Corp. Cyasorb 3638 2,2′-(1,4-Phenylene)bis[4H-3,1- CYTEC IndustriesCYASORB UV-3638 benzoxazin-4-one]

Extrusion and Molding Conditions.

Extrusions were performed either on a single screw extruder or atwin-screw extruder. Typically the D10poly(siloxane-carbonate)-containing compositions and correspondingcontrols were performed on a single or a twin screw extruder. The D30and D40 poly(siloxane-carbonate)-containing compositions andcorresponding controls were performed on a twin screw extruder.

The compositions prepared with a single screw extruder were made asfollows. All ingredients were dry blended for about 4 minutes using apaint shaker. The single screw extruder was a Sterling 1¾ inch (44.5 mm)extruder (Length/Diameter (L/D) ratio=24/1, with a vacuum port locatednear die face, with barrel and die temperature set points of 270, 275,288, 288° C.).

The compositions prepared on the 30 mm WP twin screw extruder were madeas follows. All ingredients were dry blended for about 4 minutes using apaint shaker or a drum tumbler. The twin screw extruder contained avacuum port located near die face. Typically the compositions werecompounded with an applied vacuum of 20+ inches of Hg.

The compositions prepared on a W&P 50 mm Mega twin screw were made asfollows. All additives (stabilizers and/or colorants) were dry blendedoff-line as concentrates using one of the primary polymer powders as acarrier and starve-fed via gravimetric feeder(s) into the feed throat ofthe extruder. The remaining polymer(s) were starve-fed via gravimetricfeeder(s) into the feed throat of the extruder as well. The compositionswere compounded with an applied vacuum of 20+ inches of Hg. The extruderwas a nine-barrel machine (approx. Length/Diameter (L/D) ratio=36:1)with a vacuum port located in barrel 7.

The compositions were molded after drying at 121° C. for 4 hrs on a260-ton (236 metric ton) Van Dorn or an 85 Ton Van Dorn molding machineoperating at about 300 to 320° C. with a mold temperature of about 80°C. It will be recognized by one skilled in the art that the method isnot limited to these temperatures or processing equipment.

Testing Methods.

Standard ASTM testing was performed at 50% relative humidity (RH) andunless otherwise indicated at room temperature (RT).

Notched Izod (NI-125) testing was conducted according to ASTM D 256-10on a molded sample having a 0.125 inch (3.2 mm) thickness.

Multiaxial impact (MAI) was measured at a speed of 3.3 m/s on a 3.2×102mm disc using a plunger with a hemispherical end and a diameter 12.70 mmin accordance with ASTM D3763.

Heat deflection temperature was measured on an annealed 3.2 mm sample inaccordance with ASTM D 648 using a stress of 0.455 or 1.82 MPa.

The tensile properties were measured in accordance with ASTM D638 at 50mm/min.

The flexural properties were measured in accordance with ASTM D 790 at1.27 mm/min.

In most cases melt volume ratio (MVR) was run at 300° C./ 1.2 Kg at 360second dwell.

Molecular weight was measured via GPC using polycarbonate standards.

The reported transmission data (%T) was measured at the indicatedthickness on a Gretagmacbeth Color-Eye 7000A (Propalette Optiview Goldversion 5.2.1.7) using the color space CIE1931 (Illuminant C and a 2°observer) and is equivalent to the “Y” tristimulus value.

The reported the yellowness Index (YI) data was measured at theindicated thickness on a Gretagmacbeth Color-Eye 7000A (PropaletteOptiview Gold version 5.2.1.7) in accordance with ASTM E313-73 (D1925)using Illuminant C and a 2° observer.

Heat release testing was performed on 15.2×15.2 cm plaques 1.5 mm thickusing the Ohio State University (OSU) rate-of-heat release apparatus, inaccordance with the method shown in FAR 25.853 (d), and in Appendix F,section IV (FAR F25.4). Total heat release was measured at thetwo-minute mark in kW-min/m2 (kilowatt minutes per square meter). Peakheat release was measured as kW/m2 (kilowatts per square meter). Theheat release test method is also described in the “Aircraft MaterialsFire Test Handbook” DOT/FAA/AR-00/12, Chapter 5 “Heat Release Test forCabin Materials.”

Smoke density testing (ASTM E-662-83, ASTM F-814-83, Airbus ABD0031,Boeing BSS 7239) was performed on 7.5×7.5 cm plaques of 1.5 mm thicknessaccording to the method shown in FAR 25.853 (d), and in Appendix F,section V (FAR F25.5). Smoke density was measured under flaming mode.Smoke density (Ds) at 4.0 min, and the max level (DsMax) were reported.

Low Heat Release and Low Smoke Density Compositions.

1. 1D10 (SiPC 1) Blends with TBBPA-BPA Copolymer.

Table 3 illustrates that a combination of a poly(siloxane-carbonate)having an average siloxane block length (D) of about 10 units and 1 wt %siloxane in the copolymer and a bromine-containing copolycarbonate canproduce a blend composition with excellent flame and smoke performance(EX 1-4) compared with compositions having only the brominatedcopolycarbonate (CEX 2-6), only the poly(siloxane-carbonate) (CEX 1) oronly a polycarbonate without either the poly(siloxane-carbonate) or thebrominated polycarbonate present (CEX 2).

Specifically a composition having poly(siloxane-carbonate) incombination with a polycarbonate (CEX 1) passes the smoke testing(DsMax) target of less than 200 with a value of 109 but fails the2-minute OSU test target of less than 65 kW-min/m² with a value of 68and also fails the peak OSU test target of less than 65 with a value of98. As brominated copolycarbonate is added to the composition the2-minute OSU performance and the peak OSU performance improves (EX 1-EX4) and both the target values for the 2-minute and peak OSU targetvalues are achieved (values below 65) while the smoke performance(DsMax) is maintained at passing levels (values less than 200). Thisimprovement in flame test performance was achieved with as little as 5.2wt % bromine in the composition (EX 1). In addition EX 1-EX 4 all havedensities below the targeted maximum density of 1.320 for aircraftapplications. A polycarbonate composition without thepoly(siloxane-carbonate)or the brominated copolycarbonate(CEX 2) alsofails both the 2-minute and peak OSU performance tests with values of 73and 139 although it too passes the smoke test (DsMax) with a value of139.

The benefit of the presence of siloxane in the composition isillustrated by compositions that only contain the brominatedcopolycarbonate only (CEX 3-6). They pass the OSU flame testing with2-minute values of less than 65 and the OSU peak testing with values ofless than 65 but perform very poorly in the smoke test exceeding thetarget of less than 200 with values of 561, 382 and 467.

Furthermore the clarity as measured by % transmission and % haze isexcellent for the poly(siloxane-carbonate)compositions with thebrominated copolycarbonate(EX 1-4) with transmission values of 88% orgreater and haze values of 1.2% or less. These values are as good orbetter than the polycarbonate control (CEX 2) with a transmission of 89and a % haze of 2.4. The yellowness index value, a measure of how yellowthe part appears, for EX 1 and EX 2 at 2.7 and 2.9 is also very close tothe value for the polycarbonate control 2.4. As the brominatedcopolycarbonate content increases the yellowness index increasessignificantly from 2.5 (EX 1) at 5.2% bromine content to 5.2 at 13%bromine content (EX 4). High clarity, low yellowness, and low densityvalues in combination with excellent flame and smoke performance arecritical for use of these compositions in airplane window applicationsand so higher bromine content compositions are expected to have limitedutility in window applications.

Notched Izod impact values at or near 2 ft-lbs/in (1.00 J/cm) or greatercan also provide sufficient ductility for preparation of polycarbonatesheet for use in window applications and EX 1-3 possess the targetedductility performance for window applications as well. As the brominecontents of the compositions increase the notched Izod ductilitydecreases to values less than 2 (EX 4 and CEX 5-6) and so high brominecontents in the compositions at 11% or greater would likely not beuseful in window applications.

TABLE 3 Components and Properties CEX 1 EX 1 EX 2 EX 3 EX 4 CEX 2 CEX 3CEX 4 CEX 5 CEX 6 TBBPA-BPA 0 20 30 40 50 0 20 30 40 80 SiPC 1 40 40 4040 40 PC 2 60 40 30 20 10 100 80 70 60 50 IRGAPHOS 168 0.0 0.0 0.0 0.00.0 0.0 0.0 0.0 0.0 0.0 Formulated Composition Total wt % Siloxane 0.40.4 0.4 0.4 0.4 0 0 0 0 0 Total wt % Bromine 0 5.2 7.8 10.4 13 0 5.2 7.810.4 13 ~Siloxane D Length 10 10 10 10 10 — — — — — MVR 6.5 6.0 5.6 5.65.3 6.4 6.6 6.8 6.8 6.4 NI-125, RT Ductility 100 100 0 0 0 100 100 0 0 0J/m 949 867 128 109 92 887 850 130 91 87 Ft-lbs/in 17.8 16.2 2.4 2.0 1.716.6 15.9 2.4 1.7 1.6 MAI-RT Ductility 100.0 100.0 100.0 100.0 100.0100.0 100.0 100.0 100.0 100.0 Energy to max load-Avg J 79 78 76 75 81 7575 76 78 78 Energy to failure-Avg J 91 90 89 88 89 81 81 82 84 83Energy, Total-Avg J 91 90 89 88 89 81 81 84 84 83 Density, -Avg g/cc1.194 1.239 1.268 1.288 1.314 1.198 1.242 1.265 1.289 1.315 SpecificGravity-Avg 1.197 1.242 1.271 1.291 1.317 1.198 1.243 1.266 1.290 1.316HDT 1.8 MPa 128 132 137 137 142 132 137 139 142 143 OSU Test FAR 25.853(d) Appendix F, Part IV 2 Min OSU Average 68 35 30 25 11 73 24 26 30 17Standard deviation 14 7 1 4 10 19 4 5 3 2 Peak OSU Average 98 63 54 4843 139 70 57 66 56 Standard deviation 8 4 3 2 1 14 11 5 8 14 NBS SmokeDensity (ASTM F814/E662, Flaming Mode) DsMax Ave 109 139 68 97 59 137561 382 457 304 Standard deviation 28 44 32 18 23 19 164 69 243 181Optical Properties Optical Properties % T at 62 mil (1.58 mm) 89 89 8988 88 89 89 89 88 88 YI 2.7 2.7 2.9 5.1 5.2 2.4 3.3 4.1 5.0 5.0 % Haze1.0 0.6 0.7 0.8 1.2 2.4 1.7 1.4 1.8 1.7

2. 5D10 Compositions (SiPC 2) with TBBPA-BPA Copolymer

The results in Table 4 using a poly(siloxane-carbonate)having an averagesiloxane block length of 10 units and 5 wt % siloxane in thecopolycarbonate further illustrates that a combination of polysiloxaneblock copolycarbonates and a brominated copolycarbonate outperformseither polysiloxane block co polycarbonate compositions or thebrominated polycarbonate compositions in OSU flame and smoke densitytesting.

TABLE 4 Components and Properties CEX 7 EX 5 EX 6 EX 7 EX 8 CEX 8TBBPA-BPA 0 50 70 80 90 100 SiPC 2 100 50 30 20 10 0 IRGAPHOS 168 0.060.06 0.06 0.06 0.06 0.06 Formulated Composition Total wt % Siloxane 5.02.5 1.5 1.0 0.5 0.0 Total wt % Bromine 0.0 13.0 18.2 20.8 23.4 26.0~Siloxane D Length 10 10 10 10 10 10 MVR-6 min Cc/10 min. 18.4 10.1 7.97.6 5.6 4.6 Tg ° C. 141 161 168 170 178 182 NI-125 RT Ductility 100 0 00 0 0 J/m 721 127 78 68 57 50 ft-lbs/in 13.5 2.4 1.5 1.3 1.1 0.9 MAI-RTDuctility 100 100 100 100 100 60 Energy to max load-Avg J 65 66 76 76 7777 Energy to failure-Avg J 73 72 82 82 82 83 Energy, Total-Avg 73 72 8283 82 83 Modulus of Elasticity-Avg MPa 2220 2410 2500 2620 2660 Stressat Yield-Avg MPa 58 68 72 74 77 Stress at Break-Avg MPa 50 60 61 61 65Elongation at Yield-Avg % 6 7 7 7 7 Elongation at Break-Avg % 87 105 9592 102 Flexural Modulus-Avg MPa 2100 2280 2480 2420 2450 Flex Stress at5% Strain-Avg MPa 84 93 99 98 101 Flexural Stress at Yield-Avg MPa 92106 114 113 118 Density-Avg g/cc 1.183 1.307 1.363 1.385 1.422 1.450Specific Gravity-Avg 1.186 1.310 1.367 1.388 1.426 1.454 HDT 1.8 MPa 117134 136 146 150 156 HDT 0.455 MPa 130 147 154 159 165 171 OSU Test FAR25.853 (d) Appendix F, Part IV OSU 2 Min. Average 102 40 27 34 28 26Standard deviation 11 3 6 3 6 5 OSU Peak Average 93 45 37 36 37 47Standard deviation 13 2 3 3 3 12 NBS Smoke Density (ASTM F814/E662,Flaming Mode) DsMax Ave 80.7 14.7 12.0 9.0 12.7 60.7 Standard deviation33.6 0.6 4.4 2.6 2.1 20.5 Optical Properties % T at 62 mil (1.58 mm)88.6 85.8 86.0 86.5 88.2 89.0 YI 2.8 13.4 13.1 6.4 3.8 2.9 % Haze 12.25.5 4.1 2.4 0.9 1.1

CEX 7 contains no bromine and fails both the OSU 2 min total and peakheat release tests with values greater than 65. CEX 7 in this testpassed the D_(max) flame test. CEX 8 has no siloxane present and itpasses the OSU flame and peak heat release test with values below 65 butthe D_(max) values while passing with a value below 200, However, CEX 8is extremely brittle which would make it difficult to machine and forminto parts, and has a high density, which would by deleterious to weightsavings needed to manufacture fuel efficient aircraft. By contrastcompositions having poly(siloxane-carbonate)and brominatedcopolycarbonate passed OSU flame and peak heat test with values below 65and exhibited D_(max) smoke results of less than 15 with standarddeviations below 4.4 units.

3. 6D30 (SiPC 2), 6D45 (SiPC 3) and 20D45 (SiPC 3) Compositions withTBBPA-BPA Copolymer

The flame and smoke performances of a series of compositions using abromine copolycarbonate having 26 wt % bromine atoms with siloxane blockco-polycarbonates having average siloxane chain lengths of 45 and 30 andsiloxane contents of 6 wt % in the copolymer and with apoly(siloxane-carbonate) having an average of 45 polysiloxane units and20 wt % siloxane in the copolymer are shown in Table 5.

Examples EX 9-22 illustrate that the OSU flame and heat performance aswell as smoke performance is maintained in compositions of polysiloxaneblock copolycarbonates and brominated polycarbonate copolymers withsiloxane change lengths of 30 and 45 polysiloxane units and siloxane wt% as low as 5 wt % and as high as 20 wt % in the copolymers. Comparativeexample CEX 9 and CEX 5 (Table 3) that have no poly(siloxane-carbonate)in the compositions either fail the DsMax smoke test with a value of 195and 457 or inconsistently pass as a result of high values and a highstandard deviation of 78 and 243 units, respectively. This resultillustrates once again that the presence of siloxane in the blend isnecessary to achieve consistent smoke performance pass values.

EX 16 (without heat stabilizer), when compared with EX 17 (containsimilar siloxane and bromine content as EX 16 but with heat stabilizer),demonstrates that the heat stabilizer IRGAPHOS 168 has no significanteffect on the flame or smoke performance in the compositions.

High Impact Compositions.

Formulations passing both the OSU flame and smoke tests and havingexcellent room temperature ductility performance and high flowproperties can also be achieved by some of the combinations ofbrominated polycarbonate copolymers and polysiloxane blockcopolycarbonates. For Example EX 9, 12 and 22 in Table 5 passed the2-min flame and heat release tests with flame and heat release valuesless than 65 and smoke values below 200 and showed excellent roomtemperature ductility with 100% ductility and with impact energies ofgreater than 500 J/m at high melt flow values (MVR values of 9.6-12cc/10 min.). The results from Table 5 shows that compositions withpolysiloxane content greater than 1% achieve high room temperatureimpact (both EX 14 and EX 15 have identical bromine content but EX 14has 1% polysiloxane content while EX 15 has 2 wt % polysiloxane contentand EX 14 has no ductility and room temperature while EX 15 showspartial room temperature ductility). Furthermore it is also desirablefor the compositions to have less than 13 wt % brominatedcopolycarbonate content in order to achieve high ductility (EX 9 and EX10 both have 2 wt % polysiloxane in their compositions but EX 9 has 10.4wt % bromine content from the brominated copolymer while EX 10 has 13 wt% bromine content and EX 9 has excellent room temperature impact whileEX 10 has low room temperature impact). The examples show that thepolysiloxane block copolycarbonates that have 20 wt % polysiloxanecontent are somewhat more efficient in providing high ductility and roomtemperature impact strength than the copolymers with 6 wt % content. EX9 was made from a poly(siloxane-carbonate) having 20 wt % polysiloxanein the copolymer and EX 15 was made from a poly(siloxane-carbonate)having 6 wt % polysiloxane in the copolymer, and both have identicalbromine and polysiloxane contents, but EX 9 has a higher impact andductility value than EX 15. In addition the data in Table 5 show thathigh impact values could be achieved using both the polysiloxane blockcopolycarbonates having average siloxane chain lengths of 45 and 30repeating units. Furthermore the high ductility can be achieved withcopolymers having either 20% polysiloxane content or 6% polysiloxanecontent. In the case of the polysiloxane block copolycarbonates thathave 6% polysiloxane content, it is also possible to achievetransparency. One particular benefit of the use of long siloxane chainlengths (chain lengths greater than 10 repeating units) and with about 6wt % siloxane in the poly(siloxane-carbonate) copolymer is that acombination of high impact and transparency can be achieved in additionto maintaining excellent OSU flame and smoke performance in thecompositions. Specifically EX 12 with 2 wt % siloxane and 7.8 wt %bromine content and that is formulated from apoly(siloxane-carbonate)having an average chain length of 45 siloxaneand about 6 wt % siloxane in the copolymer has 100% room temperatureductility during notched Izod testing, excellent haze with a value of3.3% and an excellent % transmission with of value of 88% while havingan OSU flame value of 46, a peak heat release value of 55 and a DsMax

TABLE 5 Components, Properties EX 9 EX 10 EX 11 EX 12 EX 13 EX 14 EX 15EX 16 TBBPA-BPA 40 50 60 30 40 40 40 40 20D45 SiPC 5 10 10 10 6D45 SiPC4 34 9 17 34 34 6D30 SiPC 3 PC1 50 40 30 36 51 43 26 26 PC 2 IRGAPHOS168 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.00 Total Wt % Siloxane 2.0 2.02.0 2.0 0.5 1.0 2.0 2.0 Formulation Wt % Bromine 10.4 13.0 15.6 7.8 10.410.4 10.4 10.4 Siloxane D Length 45 45 45 45 45 45 45 45 MVR-6 min Cc/10min. 11.1 9.7 7.5 13.6 15.8 13.7 11.4 11.4 Tg ° C. 160 162 168 156 160160 160 160 NI-125 RT Ductility 100 0 0 100 0 0 60 40 J/m 579.0 154.0136.0 646 105 122 371 304 ft-lbs/in 10.8 2.9 2.5 12.1 2.0 2.3 6.9 5.7MAI-RT Ductility 100 100 100 100 100 100 100 100 Energy to max load-AvgJ 71 74 76 75 73 77 75 75 Energy to failure-Avg J 75 77 81 82 77 82 8381 Energy, Total-Avg J 75 77 81 82 77 82 83 81 Density-Avg g/cc 1.2811.306 1.330 1.254 1.284 1.281 1.277 1.276 Specific Gravity-Avg 1.2841.309 1.333 1.257 1.287 1.284 1.280 1.279 HDT 1.8 MPa 139 141 144 128134 133 132 132 2 Min OSU Average 32 23 19 46 39 41 45 35 Std. dev. 3.21.9 4.7 5.7 3.6 6.0 4.5 2.7 Peak OSU Average 50 42 41 55 49 48 55 46Std. dev. 3.8 2.3 3.1 3.0 3.4 3.3 2.2 4.1 DsMax Ave 45 48 61 30 15 14 1829 Std. dev. 13 9 35 8 6 7 10 12 % T at 62 mil (1.58 mm) YI % Haze YI at125 mil (3.2 mm) 39 43 47 12 6 9 15 14 % T at 125 mil (3.2 mm) 29.6 27.324.1 83.1 86.7 84.8 80.8 81.6 % Haze at 125 mil (3.2 mm) 99.2 99.2 99.93.3 1.6 2.2 4.9 3.9 Components, Properties EX 17 EX 18 EX 19 EX 20 EX 21EX 22 CEX 9 TBBPA-BPA 40 50 60 70 50 40 40 20D45 SiPC 5 6D45 SiPC 4 3434 34 25 6D30 SiPC 3 42 50 PC1 26 16 6 PC 2 5 8 10 60 IRGAPHOS 168 0.060.06 0.060 0.060 0.06 0.06 0.06 Total Wt % Siloxane 2.0 2.0 2.0 1.5 2.53.0 0.0 Formulation Wt % Bromine 10.4 13.0 15.6 18.2 13.0 10.4 10.4Siloxane D Length 45 45 45 45 30 30 — MVR-6 min Cc/10 min. 10.5 9.0 7.06.0 7.3 7.7 15.4 Tg ° C. 159 163 167 171 164 161 158 NI-125 RT Ductility0 0 0 0 0 100 0 J/m 160.0 129.0 102.0 83.8 139 513.0 83.2 ft-lbs/in 3.02.4 1.9 1.6 2.6 9.6 1.6 MAI-RT Ductility 100 100 100 100 100 100 100Energy to max load-Avg J 73 73 71 73 58 72 69 Energy to failure-Avg J 7979 76 79 63 77 73 Energy, Total-Avg J 79 79 76 79 63 77 73 Density-Avgg/cc 1.281 1.307 1.329 1.360 1.305 1.277 1.291 Specific Gravity-Avg1.285 1.311 1.333 1.364 1.308 1.280 1.294 HDT 1.8 MPa 136 140 142 143136 131 139 2 Min OSU Average 27 23 20 34 32 40 28 Std. dev. 6.7 3.1 0.62.3 2 2 10.1 Peak OSU Average 47 45 42 38 33 42 54 Std. dev. 2.5 3.1 3.53.5 2 1 8.1 DsMax Ave 53 61 43 20 76 58 195 Std. dev. 22 10 12 4 55 1578 % T at 62 mil (1.58 mm) 75 79 87 YI 22.5 12.0 5.1 % Haze 14.6 12.16.6 YI at 125 mil (3.2 mm) 16 23 28 2 % T at 125 mil (3.2 mm) 79.9 72.963.9 89.3 % Haze at 125 mil (3.2 mm) 4.4 10.7 23.6 0.6smoke value of 30. EX 22 with 3.0 wt % siloxane and 10.4 wt % brominethat is formulated from a poly(siloxane-carbonate)having an averagechain length of 30 polysiloxane units and about 6 wt % siloxane in thecopolymer also shows excellent impact performance, transparency, hazeand flame and smoke performance.

Transparent Compositions.

Formulations that pass the OSU and smoke testing and that have very highpercent transmission values (greater than 85%), very low haze values(less than 2.5%) and low yellowness values (less than 6) are alsopossible to obtain using compositions of polysiloxane blockcopolycarbonates and brominated polycarbonate copolymers. Formulationswith high transmission, low haze and low yellowness index values thatpass OSU flame and smoke tests are particularly useful in windowarticles, gauge and dashboard covers and in window dust covers onaircraft. Formulations that meet the OSU flame and smoke andrequirements and that have high percent transmissions, low haze and lowyellowness index values can be obtained from a variety of polysiloxaneblock copolycarbonates with the brominated polycarbonate copolymer.Examples include EX 1, EX 2, EX 3 and EX 4 from Table 3 above preparedfrom a poly(siloxane-carbonate) having 10 polysiloxane repeating unitsand 1 wt % polysiloxane content in the copolymer; EX 5, EX 6, EX 7, andEX 8 from Table 4 above prepared from a poly(siloxane-carbonate)have 10polysiloxane repeating units and 5 wt % polysiloxane content in thecopolymer; EX 13 and EX 14 from Table 5 above prepared from apoly(siloxane-carbonate) have 45 polysiloxane repeating units and 6 wt %polysiloxane content in the copolymer and EX 22 from Table 5 aboveprepared from a poly(siloxane-carbonate) have 30 polysiloxane repeatingunits and 6 wt % polysiloxane content in the copolymer. The yellownessindex generally increases as the wt % of brominated copolycarbonate inthe compositions increases, the percent haze generally increases as thewt % polysiloxane in the composition increases and the chain length ofthe polysiloxane increases (30 and 45 polysiloxane chain lengths areworse than 10 polysiloxane chain lengths) and the % polysiloxane in thecopolymer increases (20 wt % polysiloxane in the copolymer is much worsethan 6 wt % polysiloxane) The results further suggest that thepoly(siloxane-carbonate) providing the best transparency, haze and Y1values and yellowness index values for use in window applications is thepoly(siloxane-carbonate) having approximately 10 polysiloxane repeatingunits and 1 wt % polysiloxane content in the copolymer.

Low OSU Heat Release, Low Smoke, TiO₂-Containing Compositions.

Titanium dioxide is a common additive used to increase the whiteness ofpolymer compositions. Compositions having poly(siloxane-carbonate) andbrominated copolycarbonate were prepared that also contained variousamounts of titanium dioxide in order to determine its effect on densityand stability of the polycarbonate compositions. The results are shownin Table 6.

TABLE 6 Blend Composition Components EX 23 EX 24 EX 25 EX 26 EX 27 EX 28EX 29 TBBPA-BPA 40.0 40.0 40.0 40.0 40.0 40.0 40.0 SiPC 4 50.00 50.0050.00 50.00 50.00 50.0 50.00 PC 1 10.0 10.0 10.00 10.00 10.00 10.0 10.0TiO₂ 0.0 1.0 2.0 3.0 4.0 5.0 7.0 IRGAPHOS 168 0.06 0.06 0.06 0.06 0.060.06 0.06 Total Total wt % Siloxane 3.00 3.00 3.0 3.00 3.00 3.00 3.00Formulation Total wt % Bromine 10.4 10.4 10.4 10.4 10.4 10.4 10.4 MVR-6min 8.2 8.7 8.86 8.69 8.44 8.52 8.46 MVR-18 min 8.8 9.3 9.73 9.73 9.9010.40 10.00 % MVR Change 6 min to 18 min 7.0 12.9 18.1 18.1 20.1 26.221.4 NI-125 RT Ductility 100 100 100 100 100 100 100 J/m 577 608 592 544515 520 487 ft-lbs/in 10.8 11.4 11.1 10.2 9.6 9.7 9.1 Density-Avg g/cc1.278 1.282 1.287 1.305 1.316 1.319 1.340 Specific Gravity-Avg 1.2811.286 1.290 1.308 1.319 1.322 1.343

The data in Table 6 illustrate that melt stability decreases as the TiO₂content increases (EX 24-EX 29) compared to a control that has no TiO₂present (EX 23) as measured by the change in the MVR values after 6 and18 minute heating at 300° C. To achieve 20% or less melt change, then 4PHR or less TiO₂ can be used in the polycarbonate compositions (EX 24-EX26 vs. EX 27-EX 29).

The data in Table 7 shows the effect of TiO₂ on the smoke densityperformance of a composition with and without poly(siloxane-carbonate)present.

TABLE 7 Component, Properties CEX 10 EX 30 TBBPA-BPA Copolymer 40.0 40.0SiPC 4 0.00 50.00 PC 1 60.0 10.0 TiO₂ 2.0 2.0 IRGAPHOS 168 0.060 0.060Formulated Blend Total wt % Siloxane 0 3 Composition Total wt % Bromine10.4 10.4 MVR-6 min 17.7 9.5 MVR-18 min 18.6 10.4 MVR, % Change 5.1 9.6Tg 160 161 NI-125 RT Ductility 0.0 100.0 J/m 87.7 467.0 ft-lbs/in 1.68.7 MAI-RT Ductility 100 100 Energy to max load-Average J 72 70 Energyto failure- Average J 76 76 Energy, Total- Average J 76 76 Density-Avgg/cc 1.304 1.293 Specific Gravity-Average 1.308 1.296 FAA Smoke DensityAverage 231.0 72.0 Ds at 4 min Standard deviation 78.2 43.6

The results in Table 7 show that the ability ofpoly(siloxane-carbonate)s in the compositions to reduce smoke is notdiminished by the presence of TiO₂ in the compositions, even though itis known in the art that TiO₂ can improve polycarbonate flameperformance. Even with 2 PHR TiO₂ present, without anypoly(siloxane-carbonate), CEX 10 does not pass the DsMax smoke target ofless than 200, having a value of 231. By contrast EX 30 (withpoly(siloxane-carbonate) present) passes the DsMax test target value ofless than 200 with a value of only 72.

Furthermore the impact performance of molded parts from compositionscontaining TiO₂ is improved by the presence of apoly(siloxane-carbonate) as illustrated by Ex 24-29 in Table 6 and EX 30in Table 7 (which show 100% ductility performance at room temperature)while CEX 10 has 0% ductility performance at room temperature.

Density of Low OSU Heat Release, Low Smoke Polycarbonate Compositions.

The density results in Tables 3-5 illustrate the factors that moststrongly affect the density of the compositions that do not containtitanium dioxide. The strongest influence on density is the wt % ofbromine in the polycarbonate compositions. For example in CEX 2, 3, 4,5, and 6 in Table 3 the wt % bromine increases from 0 to 13 wt % and thedensity increases from 1.198 to 1.315 g/cc. A similar trend is shown inTable 4 where the wt % bromine increases from 0 to 26 wt % and thedensity increases from 1.183 to 1.450 g/cc. The results in Table 5 abovealso illustrate that increasing the amount of siloxane in thecompositions does slightly decrease the density in the compositions. Forexample, the wt % bromine is the same in CEX 10 and EX 13-EX 15 at 10.4wt %, but the wt % siloxane increases from 0 to 2.0 wt % and the densitydecreases from 1.291 to 1.277 g/cc. The chain length of siloxane or thewt % siloxane in the poly(siloxane-carbonate)does not show a largeinfluence in the density based on the results in Table 5. In order toobtain a density below the targeted maximum density of 1.320 g/cc foraircraft applications, it appears that less than 15 wt % bromine can beused.

The presence of titanium dioxide further increases the density of thecompositions as illustrated in Table 6. In Table 6, compositions areshown having 3.0 wt % siloxane and 10.4 wt % bromine contents andincreasing amounts of titanium dioxide. In EX 23-29 the wt % titaniumdioxide increases from 0 wt % to 7 wt % and the density increases from1.278 to 1.340 g/cc. Therefore in order to achieve a maximum density ofless than 1.320, less than 5 wt % titanium dioxide can be used in thecompositions shown in Table 6.

Combining the results from the various Tables shows achieving thetargeted density maximum of 1.320 g/cc for aircraft applications can beaccomplished by balancing the amount of titanium dioxide with the amountof brominated copolycarbonate. Bromine contents of less than 13 wt % andtitanium contents of less than 5 wt % can be used to meet the aircraftdensity targets for white product compositions (EX 24-EX 27 vs. EX 28-EX29).

Alternative Bromine Sources.

Property comparisons were made between polycarbonate compositions havingsimilar wt % polysiloxane and similar wt % bromine in the compositionsusing three different bromine-containing additives, in particular abrominated epoxy oligomer (F3100 from ICL Industrial Products, EX 30), abrominated polycarbonate oligomer (BC52, EX 31) and a brominatedcopolycarbonate(TBBPA-BPA copolymer, EX 32). The results are shown inTable 8.

TABLE 8 EX 31 EX 32 EX 33 Components SiPC 4 50.0 50.0 50.0 PC 2 30.7030.00 20.00 F-3100 19.300 — — BC52 — 20.0 — TBBPA-BPA Copolymer — —40.000 Phosphite 0.060 0.060 0.060 Mw of Br compound 15,000 2,665 22,500Softening Temp C. 200 171 182 Total % 3 3 2.7 Formulation Siloxane %10.4 10.4 9.5 Bromine D length 45.0 45.0 45.0 Properties MVR-6 15.7 11.88.3 % Change 17.5 4.9 11.9 Tg 146.5 151.4 159.8 NI-125 RT Ductility100.00 0.0 100.0 J/m 773.0 123.0 744.0 ft-lbs/in 14.5 2.3 13.9 MAI-RTDuctility 100.0 100.0 100.0 Energy to J 68.1 75.1 78.4 max load-AvgEnergy to J 72.6 79.8 85.0 failure-Avg Energy, J 72.6 79.8 85.1Total-Avg Density-Avg g/cc 1.282 1.273 1.268 Specific Gravity-Avg 1.2851.276 1.271 HDT-ASTM-G  1.8 MPa 123.8 127.7 135.2 HDT-ASTM-G 0.455 MPaOSU 2 min. TTF 42.4 30.1 36.4 45.8 24.0 26.2 33.8 21.8 18.2 Average 40.725.3 26.9 Standard 6.2 4.3 9.1 deviation OSU Peak 50.5 50.5 60.3 50.843.1 49.5 59.5 60.2 54.6 Average 53.6 51.3 54.8 Standard 5.1 8.6 5.4deviation FAA Smoke Density Ds at 4 min 96.6 23.81 20.5 66.3 35.3 18.288.6 16.6 42.7 Average 83.8 26.0 27.1 Standard 15.7 13.2 13.5 deviationDmax 96.8 23.81 20.5 66.3 35.3 18.2 88.6 16.6 42.7 Ave 83.9 26.0 27.1Standard 15.7 13.2 13.5 deviation Optical Properties % T at 125 mil (3.2mm) 22.0 78.7 77.3 YI 62.7 19.1 19.8 % Haze 102.6 7.3 6.5

The results in Table 8 show that the targeted flame and smoke properties(2-min total heat release and peak heat values of less than 65 and asmoke D_(max) value of less than 200) were achieved in polycarbonatecompositions containing siloxane using the different sources of bromineas flame retardants. The high impact values in EX 31 (100% ductility inthe notched Izod test) as compared to EX 32, illustrates the importanceof selecting a bromine composition with an M_(W) of at leastapproximately 15,000 when formulations of high toughness are needed.High transparency (greater than 75%) and low haze (less than 10%) werealso found with EX 32. In addition, all three of the compositions showeddensity values below the 1.320 g/cc upper limit.

Other Additives

The effect of additives often used as flame retardants in polycarbonate,on the smoke density properties of compositions made from combinationsof the poly(siloxane-carbonate) and brominated copolycarbonate, werealso investigated and the results are shown in Table 9.

When used at levels commonly employed to improve flame performance,improve the color stability, or reduce haze in polycarbonates, theadditives showed no effect on the flame retardant performance of thepolycarbonate compositions. EX 34 (with TiO₂) possessed a similarD_(max) value to EX 35-39 (with the flame retardant, colorstabilization, or haze reducing additives) (EX 34 had a D_(max) of 21,whereas the highest D_(max) values measured for the compositions ofTable 9 was 29).

TABLE 9 Name EX 34 EX 35 EX 36 EX 37 EX 38 EX 39 TBBPA-BPA 40.0 40.040.0 40.0 40.0 40.0 SiPC 4 50.00 50.00 50.00 50.00 50.00 50.00 PC 1 10.010.0 10.0 10.0 10.0 10.0 KSS — 0.30 — — — — KSS — 0.30 — — — — Rimarsalt — — 0.08 0.08 — — Octaphenylcyclotetrasiloxane — — — 0.10 — — STB —— — — 0.75 — Phosphorus acid solution (0.15%) — — — — — 0.10 TiO₂ 2.002.00 2.00 2.00 2.00 2.00 Phosphite 0.06 0.06 0.06 0.06 0.06 0.06 TotalFormulation Wt % Siloxane 3.0 3.0 3.0 3.0 3.0 3.0 Wt % Bromine 10.4 10.410.4 10.4 10.4 10.4 Properties MVR-6 Cc/10 min 9.6 10.0 12.4 13.6 10.49.9 Tg ° C. 159 157 160 159 160 160 NI-125 RT Ductility 100 100 100 1000 100 J/m 588.0 544.0 534.0 596.0 143.0 498.0 ft-lbs/in 11.0 10.2 10.0.11.2 2.7 9.3 Density-Avg g/cc 1.287 1.291 1.291 1.288 1.293 1.291Specific Gravity-Avg 1.290 1.294 1.294 1.291 1.296 1.294 HDT-ASTM-G 1.8MPa 134 134 134 134 134 135

Other Silicone-Containing Additives.

The impact of replacing the polysiloxane block copolycarbonate withother silicone-containing additives was also investigated and theresults shown in Table 10.

TABLE 10 CEX CEX CEX CEX 11 12 13 14 Components TBBPA-BPA 30.00 30.0030.00 30.00 PC 2 70.00 69.50 69.50 69.50 DF1040 0.50 OPTS 0.50 D4 0.500Phosphite 0.060 0.060 0.060 0.060 Total Wt % 0 0.5 0.5 0.5 FormulationSiloxane Wt % 7.8 7.8 7.8 7.8 Bromine Properties MVR-6 5.5 5.9 5.5 5.6NI-125 RT Ductility 0.0 0.0 0.0 0.0 J/m 139 148 132 135 ft-lbs/in 2.62.8 2.5 2.5 Density-Avg g/cc 1.262 1.263 1.264 1.264 SpecificGravity-Avg 1.265 1.267 1.267 1.267 HDT-ASTM-G 1.8 MPa 136 135 136 135OSU Test FAR 25.853 (d) Appendix F, Part IV 2 Min OSU Average 17 59 1928 Standard 9.7 2.6 20.2 15.9 deviation Peak OSU Average 60 75 65 65Standard 4.5 4.0 3.8 8.7 deviation NBS Smoke Density (ASTM F814/E662,Flaming Mode) DS Max Ave 529 306 521 406 Standard 84 197 219 199deviation

The results in Table 10 show that none of the siloxane sources performedas well as the poly(siloxane-carbonate) of the invention. The resultsfor EX 3 and EX 4 from Table 3 (with 0.4 wt % polysiloxane content andeither 7.8 or 10 wt % bromine) show that both pass the OSU heat releaseand smoke tests, with values less than 65 for the OSU tests and lessthan 200 for the smoke tests. In contrast CEX 12, 13, and 14 haveslightly higher amounts of siloxane (0.5 wt %) and the same amount ofbromine (7.8 wt %) and fail the smoke tests with DsMax values of 300 orgreater. These other sources of silicone are therefore much lesseffective at suppressing smoke in the smoke tests thanpoly(siloxane-carbonate) described herein. While not wishing to be boundby any specific theory, it is believed that providing the siloxane in aless volatile, less mobile (higher Tg), high molecular weight polymercould help to maintain the siloxane in the composition longer and keepthe siloxane better dispersed during burning.

Color Stability and Weathering Performance.

Materials used in the transportation industry, especially those thatpass the OSU and DsMax smoke requirements, often have poor stabilitywhen exposed to outdoors light. Thus manufactures must either paint thefinished part or risk the yellowing or other discoloration of the parts.In order to demonstrate the improved color stability performance of thepoly(siloxane-carbonate) and brominated copolycarbonate compositionsover those found in art, the compositions were formulated with andwithout UV stabilization additives in a bright white color package.These compositions and results are shown in Table 11.

TABLE 11 EX 40 EX 41 EX 42 EX 43 Component TBBPA-BPA 40.0 40.0 40.0 40.0SiPC 4 50.00 50.00 50.00 50.00 PC 1 10.0 10.0 10.0 10.0 Tinuvin 1577 00.3 — — UVA 234 — 0.300 — Cyasorb 3638 — — — 0.3 TiO₂ 2.0 2.0 2.0 2.0IRGAPHOS 168 0.060 0.060 0.060 0.060 Total Total wt % 3.00 3.00 3.003.00 Formulation Siloxane Total wt % 10.4 10.4 10.4 10.4 BromineProperties MVR-6 minutes 8.9 8.7 9.4 9.0 MVR-18 minutes 8.9 11.2 10.69.0 NI-125 RT Ductility 100 100 100 100 J/m 566 542 539 525 ft-lbs/in10.6 10.1 10.1 9.8 OSU 2 min. TTF 26.0 21.3 23.0 18.3 60 mil 19.0 17.625.1 21.6 21.0 23.8 25.7 23.4 Average 22.0 20.9 24.6 21.1 Standard 3.63.1 1.4 2.6 Deviation OSU TTF 44.0 44.7 45.1 38.4 60 mil 43.2 41.8 47.349.4 44.5 43.0 44.3 48.3 Average 43.9 43.2 45.6 45.3 Standard 0.7 1.51.5 6.0 Deviation FAA Smoke De TTF 11.5 16.4 21.1 25.00 Ds at 4 minutes60 mil 10.7 16.8 22.0 22.5 11.5 27.3 23.5 20.8 Ave 11.2 20.2 22.2 22.8Standard 0.4 6.2 1.2 2.1 Deviation DsMax TTF 11.5 16.4 21.3 25.0 60 mil10.7 16.8 22.0 22.5 11.5 27.3 23.5 20.8 Ave 11.2 20.2 22.3 22.8 Standard0.4 6.2 1.1 2.1 Deviation

All of the compositions were 100% ductile in notched Izod testing, havea density requirement of less than 1.320 g/cc (data not shown), and allshowed passing values in the OSU heat release and smoke testing, withOSU values below 65 and smoke D_(max) values below 200.

Bright white sample plaques were placed on a 45 degree angle southfacing rack exposed to an unobstructed sunlight light exposure for 466hours and then tested for a color shift by measuring the reflected lightof the light-exposed plaques using a spectrophotometer. The colorstability/weathering results are shown in Table 12.

TABLE 12 Comparative EX 41 EX 43 Outdoor (a) EX 40 Tinuvin EX 42 CyasorbExposure, No UVA No UVA 1577 UVA234 3638 Hrs DE DE DE DE DE 0 — — — — —110 5.9 0.3 0.3 0.5 0.5 466 7.9 0.7 0.6 0.4 0.3 (a) White LEXAN* FST9705plaque. *Trademark of SABIC Innovative Plastics IP BV

All four of the samples (EX 40-43) of the present invention have bettercolor stability than the existing commercial OSU comparative resin. Allthree of the samples containing UV stabilizing additives showed evenlower tendency to yellow as determined by lower DE values than thesample or the sample with no UV stabilizers, even after 466 hours. Thebenefits in color stability of the compositions of the present inventioncompared to a composition that has comparable OSU smoke and flameperformance but employs polyarylate poly(siloxane-carbonate)s in thecomposition (LEXAN*FST 9705 polymer) is also illustrated by comparingthe DE values of EX 40 with FST 9705 after 466 hours of weathering(neither sample contained UV stabilization additive). The FST 9705showed much higher DE values than CEX 15 (DE 7.9 vs. 0.7).

Materials used in the following examples of thepoly(siloxane-etherimide) compositions are listed Table 13. Amounts inthese Examples are in parts by weight per hundred parts by weight of thetotal amount of polymer otherwise noted.

TABLE 13 Component Description Source PC LEXAN 100 grade SabicInnovative Plastics PEI-Siloxane A random poly(etherimide-dimethyl-Sabic Innovative siloxane) copolymer comprising Plastics structuralunits derived from m- phenylene diamine, BPADA, and an aminopropylterminated polydimeth- ylsiloxane containing on average 10 siliconatoms, with 37 ± 2 wt. % si- loxane content; Mw about 38,500 amudetermined by GPC relative to PC standards (SILTEM ® D9000) TBBPA-BPABPA and tetrabromo-BPA (50/50 wt %) was used, Mw = 23,100

The examples were prepared on 30 mm Werner Pfleiderer twin extruders asfollows. All components were dry blended for about 4 minutes using apaint shaker or a drum tumbler. The twin screw extruder contained avacuum port located near die face. The compositions were compounded withan applied vacuum of 20+ inches of Hg, and chopped into pellets aftercooling in a water bath.

The compositions are molded after drying at 121° C. for 4 hrs on a260-ton (236 metric ton) Van Dorn or an 85 Ton Van Dorn molding machineoperating at 300 to 320° C. with a mold temperature of 80° C. It will berecognized by one skilled in the art that the method is not limited tothese temperatures or processing equipment.

All the performance tests were conducted as described above.

Comparative Examples 44 and 45

Comparative examples 1 and 2 show that synergy between siloxanecontaining-resins and bromine-containing resins to achieve low heatrelease and low smoke density is not known in the art. In accordancewith U.S. Publ. 2007/0129492 (U.S. Pat. No. 7,790,292, from EX2-15), asiloxane-containing poly(ester-carbonate) copolymer was compared to acommercial composition containing the siloxane-containingpoly(ester-carbonate) copolymer and 12 wt % of a bromine-containingpolycarbonate copolymer. Results are shown in Table 14.

TABLE 14 CEX44 CEX45 Component Poly(ester-carbonate) copolymer 100 88TBBPA-BPA Copolymer 0 12.0 Total Total wt % Siloxane 1 0.88 FormulationTotal wt % Bromine 0 3.1 NBS Smoke Density ASTM F814/E662 Ds at 1.5 min1 n/a Ds at 4.0 min 23 25 DsMax 23 25 DsMax time 3.98 4

The data shows that the addition of the bromine copolymer to thesiloxane containing poly(ester-carbonate) does not yield improved smokeperformance, as in general, the results are no better or worse than thesiloxane-containing poly(ester-carbonate) without the brominatedpolymer.

Further according to US 2007/0129492, high arylate ester levels and lowpolycarbonate levels are needed to pass the OSU test. In contrast, thedata below shows that when using the composition of this invention, noarylates are needed to obtain good OSU heat release values.

Examples 46-49

These Examples show the synergistic effect of siloxane from apoly(etherimide-siloxane) and a brominated polymer on heat release andsmoke density in polycarbonate compositions. Results are shown in Table15.

TABLE 15 EX46 EX47 EX48 CEX49 Components TBBPA-BPA 40.00 40.00 40.0040.00 SILTEM 7.00 5.00 2.50 0.00 PC 53.0 55.0 57.5 60.0 Additive 0.060.06 0.06 0.0 Total Wt % 2.6 1.9 0.9 0.0 Formulation Siloxane Wt % 10.410.4 10.4 10.4 Bromine Properties MVR 6 minutes 5.5 5.6 5.7 6.8 NI-125,RT Ductility 0.0 0.0 0.0 0.0 J/m 130 119 117 90.8 ft-lbs/in 2.4 2.2 2.21.7 MAI, RT Ductility 100 100 100 100 Energy to max J 75.0 75.8 78.278.1 Energy to J 81.6 81.8 83.6 84.3 failure Energy, J 81.7 81.9 83.784.3 Total-A Density, g/cc 1.285 1.286 1.287 1.289 average HDT-ASTM-G1.8 MPa 138.4 139.7 139.7 141.5 OSU Test FAR 25.853 (d) Appendix F, PartIV 2 Min OSU Average 17 21 25 30 Standard 9.74 6 7 3 deviation Peak OSUAverage, 46 41 45 66 TTF Standard 11 6 3 8 deviation NBS Smoke Density(ASTM F814/E662, Flaming Mode) DsMax Average, 10 13 22 457 TTF Standard1 6 8 243 deviation Optical properties YI 9.8 8.2 5.6 7.1 % T at 12567.6 70.6 79.7 86.5 mil % Haze 48.5 34.0 10.9 0.7

A series of blends using a poly(etherimide-siloxane) block copolymer, abrominated polymer, and polycarbonate (EX 46-EX 48) were made andcompared to the control with no siloxane (CEX 49). Without thepoly(etherimide-siloxane) block copolymer, the smoke levels are abovethe FAA's acceptable limit of 200 for DsMax and have a high standarddeviation in the E662 test (Table 14 and FIG. 1). The peak heat releaserate in the OSU test is also above the FAA's acceptable limit of 65.With the addition of the poly(etherimide-siloxane), the smoke levelsdrop dramatically and are consistently below 25 with a low standarddeviation (Table 14 and FIG. 2). Again with the addition of thepoly(etherimide-siloxane), the peak OSU values drop and are consistently20 points below the FAA standard of 65.

In addition, the compositions have improved toughness over the control(CEX 49). The control has an impact values of less than 2 ft-lbs/in;whereas EX 46-EX 48 have impacts over 2 ft-lbs/in. All compositions are100% ductile in MAI testing at room temperature.

Ranges disclosed herein are inclusive and combinable (e.g., ranges of“up to 25 wt %, or, more specifically, 5 wt % to 20 wt %,” is inclusiveof the endpoints and all intermediate values of the ranges of “5 wt % to25 wt %,” etc.). “Combination” is inclusive of compositions, blends,mixtures, alloys, reaction products, and the like. Furthermore, theterms “first,” “second,” and the like do not denote any order, quantity,or importance, but rather are used to distinguish one element fromanother, and the terms “a” and “an” herein do not denote a limitation ofquantity, but rather denote the presence of at least one of thereferenced item. Reference throughout the specification to “anembodiment”, “another embodiment”, “an embodiment,” and so forth, meansthat a particular element (e.g., feature, structure, and/orcharacteristic) described in connection with the embodiment is includedin at least an embodiment described herein, and can or cannot be presentin other embodiments. In addition, it is to be understood that thedescribed elements can be combined in any suitable manner in the variousembodiments. The suffix “(s)” as used herein is intended to include boththe singular and the plural of the term that it modifies, therebyincluding at least one of that term (e.g., the colorant(s) includes atleast one colorants).

Compounds are described using standard nomenclature. For example, anyposition not substituted by any indicated group is understood to haveits valency filled by a bond as indicated, or a hydrogen atom. A dash(“—”) that is not between two letters or symbols is used to indicate apoint of attachment for a substituent. For example, —CHO is attachedthrough carbon of the carbonyl group. The term “alkyl” includes bothC₁₋₃₀ branched and straight chain, unsaturated aliphatic hydrocarbongroups having the specified number of carbon atoms. Examples of alkylinclude, but are not limited to, methyl, ethyl, n-propyl, i-propyl,n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, n- and s-hexyl, n-ands-heptyl, and, n- and s-octyl. The term “aryl” means an aromatic moietycontaining the specified number of carbon atoms, such as to phenyl,tropone, indanyl, or naphthyl. The term “hydrocarbon group” encompassesgroups containing the specified number of carbon atoms and havingcarbon, hydrogen, and optionally one to three heteroatoms selected fromO, S, P, and N. Hydrocarbon groups can contain saturated, unsaturated,or aromatic moieties, or a combination comprising any of the foregoing,e.g., an alkyl moiety and an aromatic moiety. Hydrocarbon groups can behalogenated, specifically chlorinated, brominated, or fluorinated,including perfluorinated. The term “aromatic group” includes groupshaving an aromatic moiety, optionally together with a saturated orunsaturated moiety.

All cited patents, patent applications, and other references areincorporated herein by reference in their entirety. However, if a termin the present application contradicts or conflicts with a term in theincorporated reference, the term from the present application takesprecedence over the conflicting term from the incorporated reference.

While the invention has been described with reference to embodiments, itwill be understood by those skilled in the art that various changes canbe made and equivalents can be substituted for elements thereof withoutdeparting from the scope of the invention. In addition, manymodifications can be made to adapt a particular situation or material tothe teachings of the invention without departing from essential scopethereof Therefore, it is intended that the invention not be limited tothe particular embodiment disclosed as the best mode contemplated forcarrying out this invention, but that the invention will include allembodiments falling within the scope of the appended claims.

We claim:
 1. A composition comprising: a first polymer comprising (a) afirst repeating unit, and (b) a poly(siloxane) block unit derived from apolysiloxane diamine or a polysiloxane dianhydride, the polysiloxaneblock unit having the formula:

wherein R is each independently a C₁-C₃₀ hydrocarbon group, and E has anaverage value of 5 to 200;derived from a polysiloxane diamine or apolysiloxane dianhydride; a second polymer different from the firstpolymer and comprising bromine; and optionally, one or more thirdpolymers different from the first polymer and second polymer; whereinthe wt % of the first polymer, second polymer, and optional one or morethird polymers sum to 100 wt %, siloxane units are present in thecomposition in an amount of at least 0.3 wt %, based on the sum of thewt % of the first, second, and optional one or more third polymers, andbromine is present in the composition in an amount of at least 7.8 wt %,based on the sum of the wt % of the first, second, and optional one ormore third polymers; and further wherein an article molded or formedfrom the composition has an OSU integrated 2 minute heat release testvalue of less than 65 kW-min/m² and a peak heat release rate of lessthan 65 kW/m² as measured using the method of FAR F25.4, in accordancewith Federal Aviation Regulation FAR 25.853 (d), and an E662 smoke testD_(max) value of less than 200 when measured at a thickness of 1.6 mm.2. The composition of claim 1, wherein the polysiloxane units of thefirst polymer is derived from a polysiloxane diamine of the formula:

wherein R is each independently a C₁-C₁₂ hydrocarbon group, R⁴ is eachindependently a C₂-C₂₀ hydrocarbon group, and E has an average value of5 to
 200. 3. The composition of claim 2, wherein R is methyl, R⁴ is1,3-propylene, and E is 5 to
 100. 4. The composition of claim 1, whereinthe poly(siloxane) block unit of the first polymer is derived from apolysiloxane dianhydride of formulas:

or a combination thereof, wherein R is each independently a C₁-C₁₂hydrocarbon group, Ar is a C₆-C₃₀ aromatic group, and E has an averagevalue of 5 to
 200. 5. The composition of claim 1, wherein the siloxaneblock unit of the first polymer is present in an amount of at least 2.0wt %, based on the weight of the first polymer.
 6. The composition ofclaim 1, wherein the bromine is present in the second polymer in anamount of at least 30 wt %, based on the weight of the second polymer.7. The composition of claim 1, wherein the first repeating unitcomprises a polyetherimide unit of the formula:

wherein R is m-phenylene, p-arylene diphenylsulfone, or a combinationcomprising at least one of the foregoing, and Z is2,2-(4-phenylene)isopropylidene.
 8. The composition of claim 1, furthercomprising an additional polymer having (a) a first repeating unit, and(b) a poly(siloxane) block unit having the formula:

wherein R is each independently a C₁-C₃₀ hydrocarbon group, and E has anaverage value of 5 to 200, wherein the additional polymer is not thesame as the first polymer.
 9. The composition of claim 1, wherein thesecond polymer is a brominated polycarbonate.
 10. The composition ofclaim 1, wherein the second polymer is a polycarbonate comprising 25 to35 mol % of units derived from 2,2′6,6′tetrabromo-4,4′-isopropylidenediphenol and 65 to 75 mole % of unitsderived from Bisphenol A.
 11. The composition of claim 1, wherein thesecond polymer is a brominated epoxy polymer.
 12. The composition ofclaim 1, further comprising an additional polymer comprising bromine,wherein the additional polymer is not the same as the first polymer orthe second polymer.
 13. The composition of claim 1, comprising 1 to 85wt % of the first polymer, and at least 15 wt % of the second polymer,each based on the total weight of the composition.
 14. The compositionof claim 1, comprising 1 to 85 wt % of the first polymer, and at least15 wt % of the brominated polymer, each based on the total weight of thecomposition
 15. The composition of claim 1, wherein the poly(siloxane)block unit is present in an amount of 1.5 to 3.5 wt % based on the sumof the wt % of the first, second, and third polymers, the bromine ispresent in an amount of 7.8 to 13 wt % based on the sum of the wt % ofthe first, second, and third polymers; and the third polymer is presentin an amount of 8 to 50 wt % based on the sum of the first, second, andthird polymers.
 16. The composition of claim 1, having a density of lessthan 1.31 g/cc.
 17. The composition of claim 1, wherein an articlemolded from the composition has a room temperature notched Izod impactof greater than 500 J/m as measured according to ASTM D 256-10 at a0.125 inch (3.2 mm) thickness.
 18. The composition of claim 1, whereinan article molded from the composition has a haze less of less than 15%and a transmission greater than 75%, each measured using the color spaceCIE1931 (Illuminant C and a 2° observer) at a 0.125 inch (3.2 mm)thickness.
 19. The composition of claim 1, further comprising 0.5 to 3parts by weight of titanium dioxide per hundred parts by weight of thesum of the first, second, and optional third polymers.
 20. Thecomposition of claim 1, wherein the composition is free of apolycarbonate consisting of carbonate units and ester units.
 21. Anarticle selected from a molded article, a foamed article, a thermoformedarticle, an extruded film, an extruded sheet, one or more layers of amulti-layer article, a substrate for a coated article or a substrate fora metallized article made from the composition of claim
 1. 22. Thearticle of claim 21, wherein the article is a component of an aircraftinterior or a train interior.
 23. The article of claim 21, wherein thearticle is selected from an access panel, access door, air flowregulator, air gasper, air grille, arm rest, baggage storage door,balcony component, cabinet wall, ceiling panel, door pull, door handle,duct housing, enclosure for an electronic device, equipment housing,equipment panel, floor panel, food cart, food tray, galley surface,handle, housing for television, light panel, magazine rack, telephonehousing, partition, part for trolley cart, seat back, seat component,railing component, seat housing, shelve, side wall, speaker housing,storage compartment, storage housing, toilet seat, tray table, tray,trim panel, window molding, window slide, or window.